Polymerization of olefinic compounds and catalysts therefor

ABSTRACT

AN ELECTROLYTIC PROCESS IS DESCRIBED FOR MAKING CERTAIN BIS-(HALOMETAL) METHANES SUCH AS BIS(DICHLOROALUMINUM)METHANE, C12A1CH2A1C12, WHICH IS A NEW COMPOUND, AND THESE COMPOUNDS CAN BE COMBINED WITH TRANSITION METAL COMPOUNDS SUCH AS VOC13 TO MAKE VERY ACTIVE CATALYSTS FOR POLYMERIZING OLEFINIC COMPOUNDS SUCH AS ETHYLENE. IN THE ELECTROLYTIC PROCESS BORON, A GROUP II, GROUP III-A OR GROUP IV-A METAL, E.G., ALUMINUM, IS USED AS AN ANODE WITH AN ELECTROLYTE SUCH AS HOA1C12 IN THE PRESENCE OF A METHYLENE DIHALIDE SUCH AS CH2C12 OR A GEM DIHALIDE WHICH DOES NOT READILY DEHYDROHALOGENATE OR ALKYLATE. IT IS PREFERRED TO CARRY OUT THE ELECTROLYSIS IN THE PRESENCE OF ETHYLENE OR ANOTHER OLEFINIC COMPOUND TO PROMOTE CONDUCTIVITY. ALSO, IT IS PREFERRED THAT ALL REACTANTS BE SUBSTANTIALLY FREE OF WATER, EXCEPT FOR SMALL KNOWN AMOUNTS OF WATER WHICH MAY BE ADDED TO PROMOTE ELECTROLYSIS. ALSO, IT IS PREFERRED TO BLANKET THE ELECTROLYSIS WITH ETHYLENE WHICH ALSO SERVES TO PROMOTE CONDUCTIVITY, OR AN INERT GAS TO EXCLUDE MOISTURE, OXYGEN AND OTHER UNDESIRABLE MATERIALS. THE CATALYSTS POLYMERIZE OLEFINIC COMPOUNDS TO LIQUID OR SOLID POLYMERS DEPENDING ON THE PARTICULAR CATALYST USED AND THE OLEFIN BEING POLYMERIZED. THE CATALYSTS ARE PROMOTED OR MODIFIED BY SMALL AMOUNTS OF WATER OR OTHER ELECTRON DONOR COMPOUNDS.

Aug. 15, 1972 POLYMERI ZATI ON OF E. H. MOTTUS E L OLEFINIC COMPOUNDSAND CATALYST THEREFOR Original F'iled March :3. 1967 United StatesPatent 015cc 3,684,739 Patented Aug. 15, 1972 3,684,739 POLYMERIZATION FOLEFINIC COMPOUNDS AND CATALYSTS THEREFOR Edward H. Mottus, 350 ClaymontDrive, Ballwin, Mo.

63011, and Morris R. Ort, 1018 Edgeworth, Kirkwood, Mo. 63122Application Mar. 2, 1967, Ser. No. 621,036, which is acontinuation-in-part of application Ser. No. 539,662, Apr. 4, 1966.Divided and this application Mar. 10, 1970, Ser. No. 23,111

Int. Cl. C08d N14 US. Cl. 252--429 A 34 Claims ABSTRACT OF THEDISCLOSURE An electrolytic process is described for making certainbis-(halometal)methanes such as bis(dichloroaluminum)- methane, Cl AlCHAlCl which is a new compound, and these compounds can be combined withtransition metal compounds such as VOCl to make very active catalystsfor polymerizing olefinic compounds such as ethylene. In theelectrolytic process boron, a Group II, Group III-A or Group IV-A metal,e.g., aluminum, is used as an anode with an electrolyte such as HOAlClin the presence of a methylene dihalide such as CH Cl or a gem dihalidewhich does not readily dehydrohalogenate or alkylate. It is preferred tocarry out the electrolysis in the presence of ethylene or anotherolefinic compound to promote conductivity. Also, it is preferred thatall reactants be substan tially free of water, except for small knownamounts of water which may be added to promote electrolysis. Also, it ispreferred to blanket the electrolysis with ethylene which also serves topromote conductivity, or an inert gas to exclude moisture, oxygen andother undesirable materials. The catalysts polymerize olefinic compoundsto liquid or solid polymers depending on the particular catalyst usedand the olefin being polymerized. The catalysts are promoted or modifiedby small amounts of water or other electron donor compounds.

This application is a division of application Ser. No. 621,036, filedMar. 2, 1967 which is a continuation-inpart of application Ser. No.539,662, filed Apr. 4, 1966 and now abandoned.

The invention relates to new catalysts and catalyst components for thepolymerization of olefinic compounds, an electrolytic process for makingthe new catalyst components, and to a process for polymerizing olefiniccompounds using these new catalysts.

The prior art related to this invention is the well-known and voluminousZiegler catalysts and polymerization art. Typical of this Ziegler art isBelgium Pat. No. 533,362, issued May 16, 1955. The most closely relatedprior art to our invention is described in US. 3,247,173, issued Apr.19, 1966, and this patent teaches the polymerization of olefiniccompounds in the presence of a catalyst containing a titanium compoundand a polymeric chemical reaction product of a methylene halide with ametal which is aluminum, zinc or magnesium. Also, since the filing ofthe parent application a publication has been made, Tetrahedron LettersNo. 21, 2315-2320 (1966), which teaches the making of one of ourcatalyst components, namely bis(dichloroaluminum)methane, and anotherrelated publication is Emschwiller Compt. Rend. 188, 1555-7 (1929).

We have now discovered new and improved catalysts for polymerizingolefinic compounds. Thene catalysts have more than one component andsome of these components, normally the major components as to amount,are novel compounds made by a unique process and which contributesvaluable solubility characteristics to the catalysts and, in addition,the activities of the catalysts are high. This solubilitycharacteristic, coupled with high activity, provides a very importantcommercial advantage of low catalyst residues in the polymer product andthe catalyst residues are more easily extracted because of solubilityor, in the case of some species of the catalysts are so active and areused in such small amounts that the catalyst residues in the polymer areinsignificant as a practical matteragain this solubility characteristiccontributes to lower than normal catalyst residues since more catalystremains in the polymerization medium when this medium is separated fromthe polymer product. This unique process for making the novel componentsof the catalysts is an electrolytic process which makes the novelcomponents in high yield, cheaply and in solution, and these componentsare directly usable without recovery from solution or further treatmentto make the catalysts and for polymerization. Further advantages,especially for a continuous polymerization process, are that the novelcatalyst components can be continuously made electrolytically and beused as made, obviating storage and stabilization problems. In thisunique electrolytic process boron, a Group II, Group III-A or Group IV-Ametal compound is made by electrolyzing a dihalide such as a methylenedihalide or a gem dihalide, which does not readily dehydrohalogenate oralkylate, in the presence of an electrolyte using an anode of boron, aGroup II, Group III-A or Group IV-A metal element of the Periodic Tableof elements.

A second component of the catalysts which are called heavy metalcompounds are salts or oxides of Group III-B, IV-B, V-B, VI-B, VII-B,VIII or I-B of the Periodic Table of elements and the heavy metalcompounds described in detail in the well-known Ziegler art are quitesuitable as components for our catalysts. In the usual Zieglercatalysts, the heavy metal compound is reduced from its highest valencestate by combination with the other catalyst component. In our catalystswhich have been studied to see if the heavy metal compound is reduced,it has been found that it was not reduced and even after thepolymerization was complete, the heavy metal compound had not beenreduced; however, it should be understood that whether or not the heavymetal compound is reduced in our catalysts may not necessarily be alimitation for them, i.e., more work would have to be done to establishthe validity of the proposition for all our catalysts.

In three copending applications of even date are describred catalysts orcatalyst components broadly or specifically covered by the claims of thepresent application. One of these application Ser. No. 621,035, filedMar. 6, 1967 and now US. Pat. 3,546,083, issued Dec. 8, 1970, teaches anelectrolytic method for making complete catalysts electrolytically or atransition metal component separately; another, application Ser. No.620,670, filed Mar. 6, 1967 and now US. Pat. 3,516,978, issued June 23,1970, teaches a chemical method of making complete catalysts chemicallyfrom alloys; and the third application Ser. No. 669,306, filed Sept. 20,1967 and now US. Pat. 3,509,189, issued Apr. 28, 1970, teaches achemical method for making the non-transition component of thecatalysts.

It is an object of this invention to provide new catalysts and catalystscomponents useful for the polymerization of olefinic compounds.

It is another object of this invention to provide a new process formaking the new catalyst components of the invention.

It is another object of this invention to provide a process forpolymerizing olefinic compounds using the new catalysts.

It is another object of this invention to provide a continuous processfor polymerizing olefinic compounds incorporating the new electrolyticprocess for making the new catalyst components.

These and other objects of the invention will be apparent as thedetailed description of the invention proceeds.

The catalyst of this invention are capable of polymerizing olefiniccompounds and particularly a-olefinically unsaturated compounds eithernon-polar or polar olefinic compounds. Normally the monomers which wepolymerize with our catalysts have not more than 20 carbon atoms sincethis includes most commercially important monomers; however, ourcatalysts will polymerize monomers having more than 20 carbon atoms. Ourcatalysts will produce solid, semi-solid or liquid polymers includingoligomers depending on reaction conditions and/or the presence ofcatalyst modifiers, chain-breaking agents and the like. The preferredsolid polymers which can be made with our catalysts have molecularweights of at least 2,000 and preferably at least 10,000; however,polymers having much higher molecular weights ranging from 20,000 to50,000 or 100,000 and even in many cases as high as 1,000,000 to3,000,000 or more can be made as desired. The molecular weights arethose calculated in the conventional manner on the basis of theviscosity of the polymers in solution as described in the Journal FiirPraktische Chemie, 2nd Series, vol. 158, 136 (1941), and J.A.C.S. 73,1901 (1951). These solid polymers generally have high density andsimilar uses in the plastics industry as the well-known Zieglerpolymers. The semi-solid or liquid polymers are useful in adhesives, aslube oil additives, gasoline additives, and the like and in general forthe same uses as are similar polymers made by conventional means.

At the present time, ethylene is by far the preferred monomer forpreparing polymers. The ethylene can be homopolymerized or can becopolymerized with varying amounts particularly of the order of 2 to 50%of higher olefins such as propylene or butylene, especially the former;however, copolymers containing less than 50% ethylene can alo be made.Our catalysts are especially useful for preparing the currently popularethylene/propylene copolymer rubbers. The ethylene-can also becopolymerized with butadiene and/or isoprene. Also of interest are thecopolymers of butadiene and/or isoprene with styrene. Homopolymers ofbutadiene, especially butadiene-1,3, homopolymers of isoprene andcopolymers of butadiene with isoprene can also be prepared with thecatalysts of our invention. With proper adjustment of catalyst ratioseither predominantly, e.g., 85% or higher, cisor transpolybutadiene canbe made using our catalyst. Other ethylenically unsaturated hydrocarbonscan also be polymerized with our catalysts and are of interest and theseare propylene, butylenes, especially butene-l, isobutylene, amylenes,l-octene, l-dodecene, l-heptadecene, l-eicosene and the like.Substituted olefins can also be polymerized by our catalysts such asvinyl cyclohexene, styrene, a-methyl styrene, vinyl naphthalene, vinylaromatic hydrocarbons generally, etc. Our catalysts are especiallydesirable for polymerizing styrene to high molecular weight polymers.Polyvinyl ethers can be made with our catalysts, especially homopolymersof alkyl vinyl ethers for example, ethyl vinyl ether, vinyl isobutylether, 2-ethylhexyl vinyl ether, etc., and copolymers of the same withethylene and other copolymerizable ethylenically unsaturated comonomerscan also be prepared. Our catalysts are especially useful forpolymerizing u-olefinic compounds. A variety of polymers of the variousmonomers named above with each other and with other comonomers can beprepared with the catalysts of our invention and the present inventionin its broadest scope includes the use of our catalysts to preparepolymers or copolymers of any olefinic compounds and even of acetyleniccompounds, e.g., acetylene.

An illustrative list of other monomers which can be polymerized by ourcatalysts is as follows: methacrylic acid and methacrylates such asmethyl methacrylate, nbutyl methacrylate, t-butyl methacrylate,Z-ethylhexyl methacrylate, lauryl methacrylate, chloroethylmethacrylate, methoxymethyl methacrylate and the like;nitrogencontaining compounds such as acrylonitrile, N-vinyl-Z-pyrrolidone, dimethylaminoethyl methacrylate, vinyl pyridine,5-methyl-2-vinyl pyridine and the like; acrylic acid and acrylatesanalogous to the methacrylates named above; other vinyl and vinylidenemonomers such as vinyl chloride, vinyl fluoride, vinylidene chloride,vinylidene fluoride, l-fluoro-l-chloroethylene, acrylonitrile andmethacrylonitrile, vinyl acetate, vinyl propionate, vinyloxyethanol,vinyl trimethyl acetate, vinyl hexanoate, vinyl laurate, vinylchloroacetate, vinyl stearate, methyl vinyl ketone; polyfluoro ethyleneof the formula CF =CXY where X is H, C1 or F and Y is C1 or F eitheralone or copolymerized with ethylene or other monomers, includingtetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene,l,1-dichloro-2,Z-difiuoroethylene and the like; especially monomercombinations such as the following for making copolymers, ethylene/vinylchloride, ethylene/indcne, ethylene/isobutylvinyl ether,ethylene/isoprene, ethylene/S-chloro-l-butene, ethylene/acenaphthylene,ethylene/cyclooctadiene-l,3 or -1,5,ethylene/vinyloxyethanol,ethylene/vinyl acetate, ethylene/cis-cyclooctene,ethylene/dicyclopentadiene, ethylene/Z-ethylhexyl acrylate, ethylene/tetrafluoro-ethylene, ethylene/ 3-methylbutene-l, ethylene/methylmethacrylate, ethylene/4-methylpentene-l, ethylene/1,3-pentadiene,ethylene/1,7-octadiene, ethylene/phenylacetylene, ethylene/vinylidenechloride, acrylonitrile/isobutylene, acrylonitrile/vinyl acetate,isobutylene/vinylidene chloride, isobutylene/ vinyl acetate, vinylacetate/vinyl methyl ether, lauryl methacrylate/ vinyl-oxyethanol,lauryl methacrylate/styrene, ethylene/ propylene/1,4-hexadiene, vinylchloride/vinyl acetate, styrene/maleic anhydride and the like; othermonomers having a plurality of ethylenic bonds, especially conjugateddouble bonds, such as 2-chl0ro-butadiene, 2-fluorobutadiene,Z-phenoxybutadiene, methacrylic anhydride, ethylene glycoldimethacrylate, diethylene glycol dimethacrylate, triethylene glycoldimethacrylate, tetraethylene glycol dimethacrylate, diethylene glycoldiacrylate, decamethylene glycol diacrylate, glycerol triacrylate,dimethacrylate esters of polyethylene glycols, diallyl maleate, vinylmethacrylate, allyl methacrylate, crotol methacrylate, methallylmethacrylate, diallyl phthalate, diallyl carbonate, diallyl adipate,diallyl fumarate, divinyl succinate, divinyl adipate, divinyl benzeneand the like; other monomers such as fumaric and maleic acids andderivatives such as maleic anhydride, monoand dialkyl esters of fumaricand maleic acids such as ethyl hydrogen fumarate, diethyl and dimethylfum-arate and maleate copolymerized with ethylene, vinyl chloride,styrene, methacrylates, :acrylates and the like; ethylene, propylene,isobutylene, 2-ethylhexenel and mixed isobutylene/vinyl isobutyl ethercopolymerized with maleic anhydride; copolymers of isobutylene withvinyl acetate, dimethyl fumarate and dimethyl maleate; copolymers ofallyl chloride with maleic anhydride; copolymers of styrene andcondensation product of maleic anhydride and ethylene glycol; copolymersof styrene with the condensation product of maleic anhydride andpropylene oxide; and, copolymers of carbon monoxide, sulfur dioxide andacetylene with ethylene.

The non-transition metal compounds of our catalysts which are made byelectrolyzing a dihalide in the presence of an electrolyte using as ananode boron or a Group II, III-A or IV-A metal are of the formula andthe monoand di-hydrohalides thereof wherein M is boron or a Group II,Group IIIA or Group IV-A metal,

X is a halogen element and n is one less than the valence of M; however,compounds of the formula where X, n and M are as defined above, R and Rtaken singly are hydrogen atoms or hydrocarbon groups preferably havingnot more than 8 carbon atoms and preferably being aliphatic and R and Rtaken together with the carbon atom to which they are attached form avinylene group in which one or both of the hydrogen atoms canalternatively be hydrocarbon groups preferably not hav ing more than 8carbon atoms and preferably being aliphatic are also catalyst componentsand can also be made by the electrolytic process provided the dihalidefrom which they are made does not readily dehydrohalogenate or alkylate.

In these compounds, M is Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg, B, Al, Ga,In, Tl, Si, Ge, Sn or Pb, X can be chlorine, bromine, iodine or fluorinebut is preferably a chlorine atom or an iodine atom. The Xs can be thesame or different halogen atoms, e.g., mixtures of chlorine and fluorineor chlorine and iodine atoms in the same compound. The hydrohalides,i.e., the monoor di-hydrohalides, of chlorine, bromine, iodine orfluorine of the M compounds described above are also usable, but thehydrochlorides or hydroiodides are preferred.

Illustrative of these XnMCMXn t,

compounds are the following:

ClzAlCHzAlClg, BI'gAlCHgAlBI'g, I AlCI-I AlI F AICH AIF ClgAlCHgAlIz,

CIBeCH BeCI, IBeCH BeI, ClMgCH MgCl IMgCH MgCI, BrMgCH MgBr, ClCaCH CaClICaCH CaI, ClSrCH SrC1, ISrCH SrI, ClBaCH BaC1 IBaCI-I BeI, ClRaCH RaCl,IRaCH RaI, CIZnCH ZnCl IZnCH ZnI, C1ZnCH ZnI, *CICdCH CdCI, ICdCHgCdIClHgCH HgCl, IHgCH HgI, Cl BCH BCl I BCH BI Cl Ga'CI-I GaCl I 'GaCH GaIClzIHCHzIDClg I2IHCH2II1I2, CIZTICHZTICIZ, Cl SiCH SiCl I SiCH SiI ClGaCH GeC1 I GeCI-I GeI ClgSHCHzSHClg, I3SIICH2SI1I3 Cl PbCH PbCl and IPbCH PbI The compounds Rx C1uM-( )-MCln 1's are the most preferred ofour catalyst components, especially Cl M-CH MCl and they are all newcompounds-n, M, R and R are as defined above. They are useful ascatalysts for the polymerization of olefins but are also useful forother purposes such as Friedel Crafts catalysts, e.g.,bis(dichloroaluminum)methane,

CIQAICHZAICIZ dissolved in methylene dichloride can be used as acatalyst to convert benzene to diphenylmethane; to promote thepolymerization of propylene oxide, and to promote the polymerization ofbenzylchloride. Most, but not all, of the compounds of the formula arealso new, e.g., H. Lehmkuhl and R. Schaefer, Tetrahedron Letters No. 21,pp. 2315-2320 (1966) describe a chemical method for preparing CI AICHAICI however, the preparation of this compound is described in ourcopending application Ser. No. 539,662, filed Apr. 4, 1966, which isprior to the Tetrahedron Letters publication. Compt. Rend. 188, 1555-7(1929) describes the chemical preparation of IZnCH ZnI and refers toother publications which describe the preparation of IMgCH MgI andBrMgcH MgBr.

Also useful for the same uses as the compounds R1 C1nM'OMG1n 2 are thecompounds formed by chemical reaction of two or more molecules of I(ulti o-MCIn 2 such as where p is an integer of 1 or more, preferably 1.A byproduct of this chemical reaction is a halide of M. The preferred ofthese compounds are the soluble ones and soluble means that the compounddissolves in the corresponding.

| Cl-C-C1 electrolytic component in an amount sutficient forpolymerization, since if the compound is not soluble it is not asdesirable and does nothave the advantages as a polymerization catalystcomponent that the compounds have. The most preferred of these compoundsare the ones where p is 0 or 1, since as p increases beyond 1 thesolubility decreases and the compounds become insoluble. An example ofthis chemical reaction is 2Cl AlCH AlCl AlCl +CI AICH AICICH AICI whichis soluble in methylene dichoride.

The compounds are made by electrolyzing a compound of the formulalengthening the time the cell could operate without electrode change.

The liquid medium for the electrolysis cell can suitably be provided byusing an excess of X-('l-X 2 over that required to make the productcompounds, alternatively a diluent such as hexane or other inert organicmedium can be used as at least part of the liquid medium for the cell.

In order to carry out the electrolysis an electrolyte is needed and anyelectrolyte that does not destroy or deactivate the catalyst can beused. The electrolyte that is preferred as X MOR X and M being definedabove and R can be H, alkyl, aryl or other organic groups, hydrocarbylbeing preferred, and especially organic groups having not more than 8carbon atoms preferred.

Perhaps the most preferred electrolyte, at least when M is Al, isdichloroaluminum hydroxide (Cl AlOH), and this electrolyte can be madeeasily by at least two methods as follows:

Five millimoles of Cl AlOH per liter of dichloromethane is sufiicientconcentration for electrolysis, and although higher concentrations wouldseem to offer no advantage, it is possible that some reducedconcentration might be more economic. AlCl itself is equally as good anelectrolyte as Cl AlOH, and aluminum chloride is dissolved in methylenedichloride by refluxing. An advantage of the aluminum chloride is thatit will react with traces of moisture in the methylene dichloride toform Cl AlOH. MnCl is also a good electrolyte and, in fact, most anymetal salt will be operable as an electrolyte in the process of theinvention, the more soluble salts being preferred. Tetraethyl ammoniumchloride is operable as an electrolyte although is inferior to AlCl andCl AlH. Water can be used as conductivity promoter for electrolytes suchas AlCl in an amount of about 0.1 to 1 mole of water per mole of AlClalthough more than this can be used.

Inert gas blanketing, e.g., N argon, helium or the like of theelectrolytic cell during electrolysis is desirable; however, it has beenfound that better conductivity and improved electrolysis are obtained ifethylene or other gaseous olefinic compound is used for blanketing thegreater part or all of the electrolysis. It may be that the ethyleneforms a complex with the cationic species of the electrolyte and therebyraises its reduction potential so the electrolyte is not lost byreduction to the metal. Problems may be caused by he presence ofethylene dissolved in the electrolyte, for example, if a complexer isusedt o premix the catalyst components before they are added to thereactor, some polymer is formed in the complexer which tends to foul thecomplexer. This problem can be solved by eliminating the complexer andcharging the catalyst components directly to the reactor wherecomplexing can be accomplished. Another solution to this problem ofpolymer formation in the complexer is to reflux the electrolysissolution to drive off the ethylene or to displace the ethylene bybubbling an inert gas through the electrolyzed solution.

The reactions involved for the preparation of compounds 31 XnMMXn arebothe electrolytic and chemical. If the reactions involving Group III-Ametals were truly electrolytic, three faradays of electricity would berequired for each gram atom of metal anode consumed. However, in ourreaction sequence only one faraday of electricity is required for eachgram atom of the metal anode consumed. The remainder of reactions arechemical. The following sequence of reactions is postulated as a routeto bis(dichloroaluminum)methane when dichloroaluminum hydroxide is theelectrolyte.

3 ClzAlOH 1 ClAlOH' Cl AlOH- Reaction at the anode ChAlOH- electronChAlOH C1- :l electron Voltage and current usage in the cell, will ofcourse, depend on the construction of the cell, the number of electrodesor electrode surface, the electrolyte and solvent combination, with thevoltage being set to make the compounds at as fast a rate as ispractical and economical. A competing entirely chemical reaction occursduring electrolysis if the current density is too low. The product ofthis chemical reaction is insoluble in dichloromethane. When the currentdensity was 0.366 amps/dm. or greater, no chemical reaction wasobserved; however, at a current density of 0.219 amps/dm. considerablechemical reaction was observed. The current densities reported weretaken from a continuous electrolysis cell, and it is possible that flowrate through the cell may also be a factor. Also, voltage is a functionof distances between anode and cathode, so cell geometry will affect theabsolute level of required voltage. The electricity supplied to the cellmay be either DC or AC. AC may have particular advantage where bothelectrodes are of the same M. The alternating current can have anydesired frequency. The frequency, however, should be sufficiently slowso that the electrochemically generated species can migrate from theelectrodes before the polarity is changed.

The electrolysis may be carried out batchwise or as a continuousoperation, the continuous operation being of particular advantage whenthe catalyst prepared electrolytically is used in a continuouspolymerization reactor.

The electrolysis may be carried out under pressure or vacuum withappropriate cell modifications; however, atmospheric pressure operationis quite suitable. The preferred temperature is 25-40" C., however,temperatures 0 to C. or even higher or lower can be used.

Aluminum alkyls and the corresponding halides and hydrides normally usedin so called Ziegler catalysts present serious handling problems sincethey are pyrophoric in air and explode when in contact with water andmany hydroxylic solvents. The compounds of this invention eliminatealmost all of the hazards of handling usually associated with Zieglercatalysts. The solutions of our catalysts as prepared by electrolysiscan be safely handled in air and can be decomposed with water and otherhydroxylic solvents since they are not pyrophoric and react mildly withhydroxylic solvents.

While the electrolysis solutions of this invention can be handled safelyin the presence of air and hydroxylic solvents, it is desirable tohandle them in inert atmospheres since a loss of catalytic activityresults when they are in contact with water or other hydroxylicsolvents.

The preferred electrolytic catalyst component is bis-(dichloroaluminum)methane. This compound is not easily isolated withoutdecomposition from the electrolyte solution in which it is made and thisis no real disability since it is conveniently used as a catalystcomponent in the solution in which it is made. These electrolyticsolutions of his- (dichloroaluminum)methane tend to lose some activityon standing; however, if the solution is refluxed for about one-halfhour to drive off excess ethylene and possibly HCl, the stability isimproved.

The usual concentration in which bis(dichloroaluminurn)methane isprepared is about 15 millimoles per liter of solvent. Concentrations of30 millimoles per liter have been prepared without problem and the upperlimit on concentration has not been established.

The second or heavy metal or transition metal compound component of thecatalysts is disclosed in many patents and publications. Probably thepreferred group of second components is disclosed in Belgium Pat. No.533,362, issued May 16, 1955, to Ziegler which discloses metal compoundsfrom the left-hand column, i.e., the B column, of the 4 to 6th groups ofthe periodic system of elements, including thorium and uranium; however,very active polymerization catalysts have been made using Groups VII-Band Group VIII metal compounds and Groups I-B and III-B also are usable;i.e., compounds of the following metals are usable; Sc, Y, La, Ce, Pr,Nd, Pm, Sm, En, Gd, Tb, Dy, H0, Er, Tm, Yb, Lu, Ac, Th, Pa, U, Np, Pu,Am, Cm, Bk, Cf, Es, Fm, Md, No, Lw, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W,Mn, Tc, Re, Fe, Ru, Os, Co, Ph, Ir, Ni, Pd, Pt, Cu, Ag and Au.Furthermore, it is preferred to use metal compounds in the highestoxidation state of the metal; however, metal compounds in loweroxidation states are usable. Preferred salts are the halides andespecially the chlorides and iodides; however, mixed halide andcyclopentadienyl compounds are very suitable in being more soluble ininert polymerization medium. An especially preferred class of heavymetal titanium compounds are the compounds of the formula (R Z),,,TiX'wherein R is a hydrogen atom or an organic group, e.g., alkyl, alkenyl,alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aralkyl, alkaryl, aryland heterocyclic, particularly hydrocarbyl, and these groups willnormally not have more than 30 carbon atoms, with alkyl having 4 to 20*carbon atoms being especially suitable. X is a halogen atom, especiallychlorine, bromine or iodine atoms. The In is an integer from 1 to 4. Zis oxygen, sulfur, selenium, tellurium, or an NR group wherein R isdefined in the same manner as R Another class of useful compounds arecomplexed titanium compounds of the formula R D-TiX wherein D is anitrogen, phosphorus, arsenic, antimony or bismuth atom and oxide orsulfide derivatives of phosphorus, arsenic or antimony, i.e., complexesof the formulas O O Ra iii'TiXt, Rs i: -TiX4, RfliiSTlXt', R b'TiX4' andthe like wherein R is defined the same as R and X is as defined above.However, other metal compounds such as the oxyhalides, acetylacetonates,etc. are also usable. Illustrative examples of suitable secondcomponents are as follows: hydroxytitanium trichloride, methoxytitaniumtrichloride, ethoxytitanium trichloride, n-propoxytitanium trichloride,isopropoxytitanium trichloride, isobutoxytitanium trichloride,t-butoxytitanium trichloride, n-butoxytitanium trichloride,dim-butoxytitanium dichloride, tri-nbutoxytitanium chloride,tetra-n-butoxytitanium, n-butoxytitanium triiodide, di-n-butoxytitaniumdiiodide, tri-n-butoxytitanium iodide, n-butoxytitanium bromide,di-n-butoxytitanium dibromide, trim-butoxytitanium bromide,ndodecyloxytitanium trichloride, n-hexadecyloxytitanium trichloride,n-dodecylthiotitanium trichloride, n-hexadecylaminotitaniumtetrachloride, n-C H PH TiC1 I1C HgBlH2TlCl4, 11-C H AsH TiClDHC4HgSbH2TlCl4, n-C H SeTiCl II-C4H TBTlCI phenoxytitanium trichloride,cyclohexyloxytitanium trichloride, benzyloxytitanium trichloride,o-pyridyloxytitanium trichloride, ethenyloxytitanium trichloride,ethynyloxytitanium trichloride, 3-cyclohexenyloxytitanium trichloride,3-cyclohexynyloxytitanium trichloride, titanium tetrachloride, titaniumtrichloride, titanium tetraiodide, titanium triiodide, titaniumtetrabromide, titanium tetrafluoride, zirconium acetylacetonate, thoriumacetylacetonate, uranium tetrachloride, vanadium III acetylacetonate,chromyl chloride (CrO Cl chromium acetylacetonate, tungsten hexachlo- 10ride, molybdenum acetylacetonate, tantalum pentachloride, zirconiumtetrabromide, K TiF titanium oxide, zirconium oxide, alkoxyhalotitaniumoxides such as n-C H OTi(O)Cl, titanium oxychloride -(Cl TiO), ClTiOTiCl Cl TiOTi(Cl) OTiCl -(CH SiOTiCl (CH SiOTiCl (OCH (CH SnOTiCl(CH3 GcOTiCl zirconium tetrabutyl, vanadium tetrachloride, vanadiumtrichloride, dicyclopentadienyl titanium dichloride, cyclopentaclienyltitanium trichloride, dicyclopentadienyl vanadium dichloride, vanadiumoxyehloride (V0Cl which is one of the most active catalyst components,polymeric compounds, e.g., those containing titanium and oxygen bonds,and the like. Also, mixtures of any two or more of the above-named heavymetal compounds will sometimes be desirable rather than using just asingle compopound, e.g., TiCl +TiI Ti-Br +-TiI or mixed components suchas TiF Cl TiCI I and the like.

Illustrative compounds of metals of Group III-B are the following: ScClYCl LaCl AcCl CoCl Thcl PI'C13, PaCl Ndclg, Uclg, PmCl Npcla, SmClPUC13, EuCl AmCl GdC1 CmCl TbCl BkCl DyCl CfCl H001 EsCl ErCl FmCl TmClMdCl YbCl Nocl LuCl LwCl the other halides, especially iodides, of theGroup III-B metals, the acetylacetonates thereof, the cyclopentadienylhalides, especially chlorides, or this oxyhalides, especially chloridesof the Group III-B meta s.

Illustrative compounds of metals of Group I-B are the following: CuClCuCl CuCl, AuCl AuCl AgCl, the other halides, especially the iodides ofthese metals, the acetylacetonates thereof, the cyclopentadienylhalides, especially chlorides thereof, or the oxyhalides, especiallyoxychlorides of the Group I-B metals.

Illustrative of the compounds of metals of Group VII-B are thefollowing: MnCl MnCl TcCl ReC1 the other halides, especially iodides ofthese metals, the acetylacetonates thereof, the cyclopentadienylhalides, especially chlorides, or the oxyhalides, especially chloridesof these Group VII-B metals.

Illustrative compounds of metals of Group VIII are the following: FeClFeCl CoCl NiCl RuCl OsCl PhCl lrCl PdCl PtCl PtCl PdCl the otherhalides, especially iodides of these metals, the acetylacetonatesthereof the cyclopentadienyl halides, especially chlorides, or theoxyhalides, especially chlorides of these Group VIII metals.

It appears that the most active heavy metal compounds to use withbis(dichloroaluminum)methane, especially for polymerizing ethylene, arethose transition metal compounds with electron donating groups such asHOTiCl C12H25OTIC13, VOC13, Vanadium acetylacetonate, chromiumacetylacetonate, iron acetylacetonate, manganese acetylacetonate, nickelacetylacetonate, cobalt acetylacetonate, vanadyl acetylacetw nate,chromyl chloride, n-C H OVCl (n-C H O) VCl (1'1-C3H70)3VC1, V2'OC13 3n-C H O) VOCl, (C H O) VO, C H OVOCl 3 3(=P l (3 )2 s (C2H5) 3N and thelike.

While the catalysts of this invention can be prepared by a variety ofprocedures, the simplest and perhaps the most effective is to add theheavy metal compound to the non-transition element compound or viceversa, preferably in the presence of an inert solvent or diluent. Themole ratio of non-transition element compound to heavy metal compound orstated another way, the mole ratio of the nontransition element to heavymetal element can vary over a wide range, suitable molar ratios ofnontransition element to heavy metal element being in the range of 0.121to 10:1 on up to 1000:1 or higher, with the preferred ratio being 0.3:1to 200:1. The optimum ratio of components will vary with the particularcomponents involved and the olefinic compound being polymerized.Suitably, the inert solvent can be the solvent or diluent in which thenon-transition element compound was prepared by electrolysis. It ispreferred to mix, suitably by mechanical stirring or otherwise, thecatalyst components as they are added one to the other, and cooling ofthe mixture can be used, if desired, especially if a substantialexothermic reaction occurs. It can also be desirable to age the catalystfrom a few minutes to an hour or even a number of hours before using forpolymerization.

A third component will be desirable for use with our catalysts sometimeswhen it is desired to make polymers which are more stereospecific. Forexample, a catalyst made by mixing or other inorganic iodide asdescribed in U.S. 3,222,347.

The catalyst is sensitive to various poisons, among which may bementioned oxygen, water, carbon dioxide, carbon monoxide, acetyleniccompounds such as acetylene, vinyl acetylene, alcohols, esters, ketones,aldehydes, and the like, although the extent to which a given quantitywill inhibit catalyst activity will be greatly dependent on theparticular material. For this reason, suitable precautions should betaken to protect the catalyst and the reaction mixture from suchmaterials. Certain of the catalysts will not be poisoned to the samedegree as other of the catalysts and this will depend somewhat on themole ratio of the non-transition element compound to the heavy metalcompound. However, the activity of some of our catalysts will even bepromoted by a limited amount of these compounds. The monomers anddiluents or solvents, if used, need not be pure so long as they arereasonably free from poisons. It is well to protect the catalyst duringpreparation, storage, and use by blanketing with an inert gas, e.g.,nitrogen, argon or helium. However, in other instances, blanketing withthe monomer being polymerized is as suitable or more preferable thanblanketing with an inert gas.

As in the case of Ziegler catalysts, minor amounts of third componentsto modify catalyst activity can be added to our catalysts. Modify meansthat the catalyst activity may be either increased (promoted) ordecreased by these third components, and/ or the third components mayalso have an effect on the properties of the polymer produced from thecatalyst. As an alternative to adding the modifier to the preparedcatalyst, the modifier can be added to the heavy metal compound prior tothe time the heavy metal compound is added to the nontransition elementcompound; however, normally it will be preferred to add the modifierafter the non-transition element compound and the heavy metal compoundhave been added together to form our catalyst. One such modifier is athiophenol as described in US. 3,009,908. This thiophenol should beadded in an amount sufficient to modify the catalyst activity butinsufficient to kill the catalyst activity, preferably in the range of0.1 to 2 moles of thiophenol per mole of non-transition element compoundin the catalyst. Another suitable modifier is a mercaptan as describedin US. 2,996,459, and this modifier can be added to our catalyst in asimilar manner as the thiophenol in an amount preferably in the range of0.1 to 1.5 moles of mercaptan to non-transition element compound,insuflicient to kill the catalyst activity. Another suitable modifier isa phenol as described in US. 3,150,122, and this modifier can be addedto our catalyst in a similar manner as the thiophenol in an amountpreferably in the range of 0.1 to 5 moles per mole of non-transitionelement compound, sufficient modifier being added to change the activityof the catalyst but insufficient to kill the catalyst. Other suitablemodifiers are reactive organic oxygen compounds such as al cohols,ketones, aldehydes and organic acids as described in U.S. 3,163,611which can be added to our catalysts in a similar manner as thethiophenols in an amount preferably in the range of 0.1 to 1.5 moles oforganic compound per mole of non-transition compound, sulficientmodifier being added to change the activity of the catalyst butinsufiicient to kill the catalyst activity. Another suitable modifier isa strong acid such as described in copending application Ser. No.760,858, filed Sept. 15, 1958, and this strong acid modifier can beadded to our catalysts in a similar manner as the thiophenols in anamount preferably in the range of 0.5 to 3 moles of strong acid per moleof non-transition element compound, sufiicient modifier being added tochange the catalyst activity but not kill the activity, and hydrochloricacid is one of the preferred species of strong acids although the otherhydrogen halide acids such as hydrobromic, hydroiodic and hydrofluoricacid, as well as sulfuric, etc., can be used as modifiers. Water isanother suitable modifier for our catalysts, the use of water as amodifier is described in U.S. 3,184,416 for Ziegler catalysts, and watercan be added to modify the activity of our catalysts in a similar manneras thiophenol in an amount in the range of 0.01 to 2.0 mole of Water permole of non-transition element compound, sufficient water being used tochange the catalyst activity but not kill it; however, for ourcatalysts, it is preferred to use about 0.1 to 1.5 moles of water permole of non-transition element compound going to make up the catalystalthough more than this can be used. In addition to water, alcohols,phenols, mercaptans, thiophenols, aldehydes and the like, which areelectron donating compounds useful as modifiers for our catalysts, otherelectron donating compounds such as amines, arsenes, stibenes,phosphines and the like are also useful as modifiers or promoters forour catalysts and should be used in similar amounts, i.e., in the rangeof about 0.01 to 3 moles per mole of non-transition element compound,sufficient amount being used to modify or promote, but not kill,catalyst activity. Theory regarding electrondonating compounds isdiscussed in Inorganic Chemistry by Kleinberg, Argersinger and Griswold,p. 218 (1960). The method of adding the catalyst modifiers is notcritical; however, preferred methods of adding are to add the modifierto the catalyst after the two main components have been added together,to add the modifier to the heavy metal component, or to make the heavymetal component of the catalyst with the modifier incorporated thereinby chemical reaction. The third components listed above in thisparagraph are as indicated in the previous paragraph catalyst poisonsand if added to the catalyst in sufiiciently large quantities willcompletely kill catalyst activity; however, if added to the catalyst insmall controlled quantities as indicated in this paragraph, they modifyor promote catalyst activity and also the properties of the polymersproduced from the modified catalysts. Hydrogen has been found to beeffective as a catalyst and/ or polymer modifier, especially in thepresence of VOCl catalyst component during polymerization of ethylene toraise the melt index of the polyethylene. Acetylene, like hydrogen, canbe used as a catalyst and/ or polymer modifier, e.g., 200 to 300 p.p.m.of acetylene in ethylene will give polyethylene of modified properties.Another type of additives for the catalysts of the invention is anon-ionic surfactant which tends to stabilize the catalyst and preventloss of catalyst activity with age as indicated in US. 3,060,132 and thenon-ionic surfactant is preferably added to the catalyst in an amount inthe range of 0.1 to 10% by weight based on the catalyst.

Normally, catalysts of the invention will be used for polymerizationdissolved or suspended in inert organic liquids such as the liquids inwhich the catalysts were prepared or in the presence of other addedsolvent. Such solvents for polymerization can suitably be saturatedaliphatic and alicyclic, aromatic hydrocarbons and halogenatedhydrocarbons. By way of example can be mentioned liquefied propane,iso-butane, normal butane, nhexane, the various isomeric hexanes,n-heptane, cyclohexane, methylcyclopentane, dimethylcyclohexane,dodecane, industrial solvents composed of saturated and/ or aromatichydrocarbons, such as kerosenes, naphthas, etc., especially whenhydrogenated to remove any olefin compounds and other impurities, andespecially those ranging in boiling point up to 600 F. Also, benzene,toluene, ethylbenzene, any of the xylenes, cumene, decalin, ethylenedichloride, chlorobenzene, carbon tetrachloride, chloroform,dichloromethane and o-dichlorobenzene. In some instances, it is alsoadvantageous to prepare the catalyst in the presence of a monomer, oreven the monomer to be polymerized.

Polymerization can readily be effected in the presence of any of theclasses of solvents and specific solvents just named, or mixturesthereof. If the proportion of such solvents is kept low in the reactionmixture, such as from to 0.5 part by weight inert organic solvent (i.e.inert to the reactants and catalysts under the conditions employed) perone part by weight of total polymer produced, solvent recovery steps areobviated or minimized with consequent advantage. It is often helpful inobtaining eificient contact between monomers and catalysts in aidingremoval of heat of reaction to employ larger amounts of solvent, forexample, from to 30 parts or more by weight of solvent per one part byweight of total polymer produced. These inert solvents, which aresolvents for the monomers, some or all of the catalyst components andsome of the polymers, but are non-solvent for many of the polymers, forexample polyethylene, can also properly be termed inert liquid diluentsor inert organic liquids.

The amount of catalyst required is dependent on the other variables ofthe particular polymerization reaction and/ or monomer being polymerizedand although amounts as small as 0.00005 or less weight percent based ontotal weight of monomers charged are sometimes permissible, it isusually desirable to use somewhat larger amounts, such as from 0.0001 upto 2 to 5% or considerably higher, say up to 20%, depending on themonomer or monomers being polymerized, the particular catalystcomponents, the presence or absence of solvent, the temperature,pressure and other reaction conditions. When polymerization is effectedin the presence of a solvent a catalyst to solvent volume ratio may varywidely at from about grams per liter to 5 grams per liter. By using assmall an amount of catalyt as is economically feasible, problems ofremoving catalyst from polymer product are minimized or obviated.

The polymerization can be effected over a wide range of temperatures,again the particular preferred temperature being chosen in accordancewith the monomer, pressure, particular catalyst and other reactionvariables. For many monomers, from room temperature down to say --40 C.or even lower, are suitable and in many cases it is preferred that thetemperature be maintained at below about 35 C. However, for othermonomers, particularly ethylene, higher temperatures appear to beoptimum, say from 50 to 90 C. Temperatures ranging up to 100 C. andhigher are generally satisfactory for polymerization with our catalyst.

The pressure at which the polymerization is carried out is dependentupon the chosen monomer, or monomers, as Well as other variables. Inmost instances the polymerization is suitably carried out at atmosphericpressure or higher. Although sub-atmospheric pressures are permissiblethere would seldom be any advantage. Pressures ranging from atmosphericto several hundred or even many thousand pounds per square inch gauge,e.g., 5,000 p.s.i.g. and higher are suitable. Actually, for the pressurepolymerizations, pressures from 2 to 10 atmospheres are sufiicient andpreferable in polymerizing ethylene. While high pressures are notrequired in order to obtain the reaction, they will have a desirableeifect on the reaction and, in some instances, on polymer quality. Achoice of whether or not to use an appreciably elevated pressure will beone of economic and practical consideration, taking into account theadvantages that can be obtained thereby.

The monomer or mixture of monomers is contacted with the catalyst in anyconvenient manner, preferably by bringing the catalyst and monomertogether with intimate agitation provided by suitable stirring or othermeans. The agitation can be continued during the polymerization, or insome instances, the polymerization mixture can be allowed to remainquiescent while the polymerization takes place. In the case of morerapid reactions with more active catalysts, means can be provided forrefluxing monomer and solvent, if any of the latter is present, and thusremove the heat of reaction. In any event, adequate means should beprovided for dissipating the exothermic heat of polymerization, ifnecessary. If desired, the monomer can be brought in vapor phase intocontact with the solid catalyst, in the presence or absence of liquidsolvent. The polymerization can be effected in the batch manner, or in acontinuous manner, such as for example, by pass ing the reaction mixturethrough an elongated reaction tube which can be contacted externallywith suitable cooling medium to maintain the desired reactiontemperature.

The time of contact of the monomer with catalyst will vary depending onthe other reaction conditions, the monomer or monomers beingpolymerized, the particular catalyst being used, the degree ofpolymerization desired, etc. Generally, the time will vary from a fewminutes to a number of hours; however, it can in some cases run to anumber of days.

The polymer can be recovered from the total reaction mixture by a widevariety of procedures, chosen in accordance with the properties of theparticular polymer, the presence or absence of solvent, and the like. Itis generally quite desirable to remove as much catalyst from the polymeras possible and this is conveniently done by contacting the totalreaction mixture or the polymer after separation of the solvent, with ahydrocarbon or halogenated hydrocarbon, with methanolic hydrochloricacid, with an aliphatic alcohol such as methanol, isobutanol, secondarybutanol, or by various other procedures or combinations of thesecatalyst removing agents. If the polymer is insoluble in the solvent itcan be separated therefrom by filtration, centrifuging or other suitablephysical separation procedures. If the polymerization is carried out inthe presence of a solvent, as will normally be the case, and the polymeris insoluble in the solvent most of the catalyst will be removed fromthe polymer by filtration to remove the solvent with catalyst dissolvedtherein, then washing the polymer one or more times with thepolymerization solvent and/or other medium is a particularly desirablemethod of reducing further the catalyst level in the polymer. AfterWashing the polymer with the polymerization medium, it may be desirableto kill the activity of any catalyst remaining in the polymer bytreating the polymer with an aliphatic alcohol such as methanol. If thepolymer is soluble in the solvent, it is advantageously precipitated byadding to the solution a non-solvent usually being an organic liquidmiscible with the solvent but in which the polymer to be recovered isnot readily soluble. 'Of course, any solvent present can also beseparated from the polymer by evaporation of the solvent, care beingtaken to avoid subjecting the polymer to a temperature so high as tocause deterioration of the polymer in such an operation. If a higherboiling solvent is used, it may be desirable to finish any washing ofthe polymer with a low boiling material such as one of the aliphaticalcohols or hexane, pentane, etc. which aids removal of the higherboiling 15 materials and permits the maximum removal of extraneousmaterials during the final polymer drying step. Such a drying step isdesirably efifected in a vacuum at moderate temperatures, preferablywell below 100 C.

For conventional catalysts such as the Ziegler catalysts, treatment oftheir polymer products to remove catalyst residues is an expensive andnecessary operation. The catalysts of the present invention haveextremely high catalyst activity giving very high yields of polymerproduct per gram of catalyst, and also these catalysts have a highdegree of solubility normally being soluble in the methylene dihalide inwhich they are made. These catalysts of the invention in general aremore soluble than the Ziegler catalysts which are usually used assuspensions rather than solutions for polymerization, and at least thechlorides will usually be soluble in the methylene dichloride in whichthey are made in sufficient concentrations for polymerization, althoughobviously they can be used as suspensions as are the Ziegler catalysts.As a result, small amounts of catalyst can be used and most of thecatalyst is removed from the polymer in the liquid polymerizationsolvent when the solvent is separated from the polymer product. As apractical matter, the catalyst residues in the polymer products areinsignificant and no further treatment of the polymer product to removecatalyst residues is usually necessary. Thus, our polymer product cannormally be recovered inexpensively by any one of a number ofalternative methods, for example: (1) the polymer slurry from thepolymerization reactor can go directly to a drier where the liquidpolymerization medium, such as hexane or methylene dichloride, isevaporated off and the dried polymer finished product is produced, (2)most of the liquid can be removed from the polymer slurry in acentrifuge or filter and then the balance can be removed in a drier, or(3) most of the liquid can be removed in the centrifuge or filter, thepolymer cake can be washed on the centrifuge or filter to further reducecatalyst levels in the polymer and then the polymer cake can be dried.Normally, when using a Ziegler catalyst such as Al*(C H +-TiC1 thepolymer would have to be subjected to a multistage washing techniquesuch as described in U. S. 3,074,921 to reduce catalyst levels to anaccepted level.

The invention will be more clearly understood from the followingdetailed description of specific examples thereof read in conjunctionwith the accompanying drawing wherein a continuous process for producingsolid ethylene polymer is described. Pumps and valves have not beenshown in the attached drawing since it is intended to be a flow diagramand startup of the process is not described but rather operation afterthe process has been lined out and is operating continuously.

Vessel 1 is an electrolytic cell, 2 is an aluminum anode, 3 is analuminum cathode and stirrer 4 is provided for agitation. Line 21 is forthe purpose of introducing ethylene to blanket the reaction in theelectrolysis cell and line 22 is for the purpose of venting ethylene.Into the electrolysis cell through line 20 is introduced apre-electrolysis solution consisting of methylene dichloride, aluminumtrichloride and an equimolar amount of water based on the aluminumtrichloride. The ethylene introduced to the electrolysis cell serves notonly to blanket the reaction but also to promote the conductivity in thecell. The direct current flowing through the cell is adjusted to asufliciently high level to avoid the formation of any substantialamounts of strictly chemical catalysts.

Bis(dichloroaluminum)methane made in the electrolytic cell is sent vialine 23 to complexer 5 which is provided with a stirrer 6. Through line24 VOCl dissolved in methylene dichloride is introduced to the complexerand the two components of the catalyst are stirred in the complexer forabout 5 minutes before being introduced to the polymerization reactor.It is preferred that the bis(dichloroaluminum)methane dissolved inmethylene dichloride be substantially purged of ethyl- 16 ene bynitrogen or by refluxing prior to introduction into the complexer toavoid formation of polyethylene in the complexer.

Catalyst is charged via line 25 to polymerization vessel 7 which isagitated by stirrer 8. Through line 26 ethylene, containing about 20volume percent hydrogen, is continuously charged to vessel 7 and throughline 27 makeup hexane is charged to vessel 7. From the top of thepolymerization vessel through line 28 ethylene which has not beenpolymerized plus some vaporized dichloromethane and hexane flow tocondenser 9. From condenser 9 gaseous ethylene goes through line 29 t0compressor 10 which delivers the ethylene back to polymerization vessel7 through line 31. Through line 30 condensed hexane and methylenedichloride from condenser 6 go to enclosed basket centrifuge 11 for thepurpose of Washing centrifuged polyethylene cake. Alternatively, if itis decided not necessary or desirable to wash the polyethylene cake inthe centrifuge, the condensed hexane and methylene dichloride can bereturned directly to the polymerization vessel.

From the bottom of polymerization vessel 7 a slurry of polyethylene inhexane and methylene dichloride is taken through line 32 and introducedto centrifuge 11. From centrifuge 11, via line 33, hexane and methylenedichloride containing catalyst which has been separated form thepolyethylene is returned to the polymerization vessel, and under suchconditions only makeup catalyst need be added to the polymerizationvessel via line 25. Alternatively, if it is not desired to re-usecatalyst recovered from the centrifuge, the hexane and methylenedichloride containing the catalyst can be distilled to remove thecatalyst, the solvent condensed and returned to the polymerizationvessel.

The polyethylene separated from the slurry in centrifuge is Withdrawnfrom the centrifuge via line 34 and goes to dryer 12. In dryer 12 thehexane and methylene dichloride remaining with the polyethylene areevaporated and taken via line 36 to condenser 13. The condensedmethylene dichloride and hexane from condenser 13 are returned to thepolymerization vessel via line37. From dryer 12 the dried polyethyleneproduct is removed via line 35. An alternative method of operating is tobypass centrifuge 11 with the slurry in line 32 and charge the slurrydirectly to dryer 12. In these continuous processes, methylenedichloride introduced into the system with fresh catalyst would build upover a period of time and it might be desired eventually to purify thesolvent in the system by distillation to reduce the methylene dichloridelevel; however, methylene dichloride is as good a polymerization mediumas hexane.

EXAMPLE 1 To a 250 ml. flask enclosed in a nitrogen atmosphere box Wasadded 0.15 g. of sublimed, anhydrous aluminum chloride (A101 Then to theflask was added 200 ml. of anhydrous dichloromethane using a nitrogenblanket. The aluminum chloride was dissolved in the dichloromethane anda clear colorless solution resulted.

A glass electrolysis vessel Was prepared having a nitrogen or other gasinlet and outlet and a Water condenser outlet at the top. The electrodesconsisted of aluminum foil concentric hollow cylinders, the cathodebeing of smaller diameter and being located within the anode. A Tefloncoated magnetic stirring bar was provided for agitation of theelectrolysis cell. Each component of the cell was cleaned and driedbefore assembling, then purged with nitrogen after assembly.

To the electrolysis cell was then added m1. of the aluminumchloride/dichloromethane solution described above. The power supply wasturned on and electrolysis was carried out for a period of three hours.Voltages were increased from 250 to 500 volts during the run in anattempt to maintain a constant 50 milliamps current; however, by the endof the run the current had dropped to 30 milliamps. All during the runnitrogen flowed through the cell maintaining a nitrogen blanket. At theend of the run ml. of additional dichloromethane was added to make uplosses during electrolysis.

The amount of electricity used in the electrolysis was determined to be3.6 milli (m) faradays. Anode loss determined by weighing before andafter electrolysis was 0.1234 g. (4.6 mmoles). There was aninsignificant weight gain for the cathode.

The electrolyzed solution was then added to the polymerization vesselwhich already contained 0.5 g. (2.0 mmoles) of dicyclopentadienyltitanium dichloride. The contents of the polymerization vessel werestirred and ethylene was passed through the mixture for 1.0 hour. At theend of the 1.0 hour of polymerization, the polymerization mixture wasquenched with methanol by adding the polymerization mixture to about 250ml. of methanol. The polymer product precipitated and was separated byfiltration. Dry polymer yield was 1.62 g. The polymer showedcrystallinity and it melted at 125-126 C. The polymer had a specificviscosity of 0.025 which calculated to a molecular weight ofapproximately 6,500. It was later discovered that in some of these earlyruns all of the reactants were not as dry as desirable, althoughattempts were made to exclude water except in controlled amounts, sothese runs show operability of the process but not necessarily optimumconditions.

EXAMPLE 2 This example describes an experiment in which methanol wasadded to the aluminum chloride solution in dichloromethane to providethe electrolyte solution. 0.15 g. of aluminum chloride in 200 ml. ofmethylene dichloride was prepared and 0.045 ml. of methanol was added.This electrolyte solution then has a 1 aluminum: 1 methoxy molar ratio.The ingredients were mixed until all the aluminum chloride had dissolvedand a homogeneous solution resulted.

The electrolyte solution is electrolyzed and used to polymerizeethylene. This experiment was carried out in similar equipment and in asimilar manner to the experiment of Example 1. 100 ml. of theelectrolyte solution was added to the electrolysis cell. Theelectrolysis was carried out with nitrogen blanketing being changed toethylene blanketing after six minutes of electrolysis. 1.94 mfaradayswere used during the electrolysis and 1.99 mmoles of aluminum wereremoved from the anode. During electrolysis 0.0519 amp-hrs. ofelectricity were used.

After the electrolysis 0.5 g. of dicyclopentadienyl-titanium dichloridewas added to the electrolyzed solution in a polymerization vessel.Polymerization was carried out for one hour in similar equipment andsimilar manner to Example 1 and the polymerization mixture was quenchedin the usual manner with methanol. The yield of polymer was 2.07 g. andthe polymer had a melting point between 129 and 131 C. The specificviscosity of the polymer was about 0.071 which calculates to a molecularweight of 23,000.

EXAMPLE 3 The following example describes a treatment of the polymer toremove the catalyst therefrom. A stock electrolysis solution havingmolar ratio of AH OzlAlCl in CH Cl was used in this experiment in theelectrolysis cell. Electrolysis was carried out in a similar manner toExample 1. 1.03 mmoles of aluminum were lost from the anode. Theelectricity used in the electrolysis was 1.02 mfaradays. Nitrogenblanketing was used during entire electrolysis.

Polymerization was carried out in a similar manner to Example 1. Thetitanium compound used was dicyclopentadienyltitanium dichloride with aTi to Al ratio of 0.9/1.0. After the polymerization was completed thepolymerization mixture was transferred under nitrogen to a 1 literseparatory funnel and 100 ml. of additional methylene dichloride wasadded. After shaking the mix ture, the polymer floated on top and theliquid solution was drained from the polymer. The polymer was thenWashed in the separatory funnel with eight separate 25 ml. portions ofmethylene dichloride. Finally the polymer was washed with about 500 ml.of methanol. The polymer was then filtered and dried to constant weightto give 1.43 g. of polymer having a melting point of 128.5132.5 C. Asample of the polymer was submitted for titanium and aluminum analysisand the polymer was found to contain 15 ppm. of aluminum and 18 ppm. oftitanium.

EXAMPLE 4 This experiment describes the polymerization of ethylene usingthe electrolytic catalyst plus cyclopentadienyltitanium trichloride asthe titanium source. This experiment was carried out in a similar mannerto Example 1, except as indicated below. The amount of water was 0.75 HO:1AlCl molar ratio in the electrolyte and in the electrolysis anitrogen blanket was used during the entire electrolysis. The electriccurrent used was 1.03 mfaradays. 1.48 mmoles of aluminum was lost fromthe anode.

The aluminum/titanium ratio was 2.1/1 with cyclopentadienyl titaniumtrichloride being the titanium compound used. The polymerization was forone hour as usual and the yield of polymer was 5.11 g. having a meltingpoint of 130-132 C.

EXAMPLE 5 This example describes the use of dicyclopentadienyl vanadiumdichloride rather than the corresponding titanium compound with anelectrolyzed solution to polymerize ethylene. The solution prepared forelectrolysis was made up as follows: 0.268 g. (0.002 mole) of freshlysublimed aluminum chloride and 36 ml. (0.002 mole) of distilled waterwere added to 400 ml. of methylene dichloride which had been carefullypurified by distillation and drying. Then ml. of this electrolysissolution was added to the electrolysis cell using nitrogen blanketing.Ethylene was bubbled through the electrolysis cell both before andduring the electrolysis. The time of the electrolysis was 64 minutes andabout 50 milliamps constant current was maintained during theelectrolysis. An additional 8 ml. of dry methylene dichloride was addedafter 45 minutes of electrolysis. During the electrolysis, 2.0 mfaradaysof electricity were used. The aluminum loss from the anode was 0.0433 g.

To the electrolyzed solution was added 0.16 mmole (0.04 g.) ofdicyclopentadienyl vanadium dichloride Cp VCl (to give an Al/V molarratio of 10). After 10 minutes of stirring with nitrogen blanketing thevanadium compound was still not in solution, however, ethylene was addedto start the polymerization. Polymerization was continued for two hoursafter which time the polymerization mixture 'was quenched and thepolymer worked up in the usual fashion. Yield of polymer was 2.68 g.having a softening point from about -440 0., however, the polymer hadnot melted at 200 C. The polymer is rubbery at 200 C.

EXAMPLE 6 This example describes the use of vanadium oxychloride (V001in conjunction with the usual electrolyzed aluminum solution topolymerize ethylene. From the same stock solution used to prepare theelectrolyte in Example 5 the electrolyte for this example was obtained.100 ml. of this electrolysis stock solution was used. It was added tothe electrolysis cell with nitrogen blanketing, then ethylene wasbubbled through the electrolysis solution both before and duringelectrolysis. The time of electrolysis was 64 minutes and a constantcurrent of about 50 milliamps was maintained during the electrolysis.During the electrolysis, 2 additional 10 ml. portions of dry methylenedichloride were added to the electrolysis cell. Loss of aluminum fromthe anode during electrolysis was 0.0459 g. and 2.0 mfaradays ofelectricity was passed during electrolysis.

To the electrolyzed solution was added 0.17 mmole (0.0295 g. equal0.0161 ml.) of VOCl giving a molar ratio of 1:1 of Al to V. Ethyleneflow was then started and continued for 30 minutes at which time thepolymerization mixture was almost too thick because of the polymerformed to continue the polymerization. The polymerization mixture wasthen quenched and the polymer worked up in the usual manner. The yieldof the polymer was 2.93 g. and the polymer had a softening point between130 and 140 C. but did not melt even at 200 C. at which temperature itis a rubber. The polymer is soluble in hot xylene.

EXAMPLE 7 This example describes the polymerization of butadiene using acatalyst formed by mixing titanium tetraiodide (TiI with an electrolyzedaluminum component. The electrolysis solution was prepared by adding0.15 g. of aluminum chloride (0.00113 mole) and 0.020 g. of water(0.00113 mole) to 200 ml. of purified and dried methylene dichlorideresulting in an aluminum/water molar ratio of lAlzlH O. 100 ml. of thissolution was charged to the electrolysis vessel with nitrogenblanketing. During this first six minutes of electrolysis the cell wasblanketed with nitrogen but at the end of this time, ethylene was usedto blanket the cell for the balance of the electrolysis. Totalelectrolysis time was 75 minutes and constant current of about 0.05 ampwere maintained during the electrolysis. At the end of the electrolysisthe cell was again blanketed with nitrogen and the ethylene blanketingstopped.

To the electrolyzed mixture was added 0.6 g. (2 mmoles) of titaniumtetraiodide. Butadiene was then added to the electrolysis cell for onehour. At the end of the hour of polymerization the polymerizationmixture was quenched and the polymer worked up in the usual manner.Yield of dry solid polymer was 4.74 g.

EXAMPLE 8 This example teaches the use of the mother liquor from a priorpolymerization with a fresh electrolysis solution to polymerizeethylene. The first experiment to prepare the mother liquor for use inthe polymerization of this experiment was as follows: A stock solutionof the electrolyte was made up as follows: 0.34 g. (2.54 mmole) ofaluminum chloride and 0.052 ml. (1.27 mmole) of methanol was added to450 ml. of methylene dichloride. An aliquot of 100 ml. of this stocksolution was added to the electrolysis cell. The electrolysis wascarried out using ethylene blanketing of the electrolysis cell for 33minutes and a constant current of about 50 milliamps was maintainedduring this time. 1.0 mfaradays of electricity was used in theelectrolysis. The anode lost 0.86 mmoles of aluminum.

0.43 mmoles (0.11 g.) of dicyclopentadienyl titanium dichloride wasadded to the electrolyzed solution to give an aluminum to titanium ratioof 2AlzlTi. Polymerization of the ethylene was carried on for one hourand then the polymer was separated by filtration from the mother liquor.

Below is described the experiment in which the mother liquor was used.To the electrolysis vessel was charged 100 ml. of the same stocksolution of electrolyte as is described in the paragraph above of thisexample. The electrolysis cell was blanketed with ethylene andelectrolysis was conducted for 45 minutes. 1.02 mfaradays of electricitywas used and the anode loss was 1.06 millimoles of aluminum. Theelectrolyzed solution was added to the mother liquor from thepolymerization described in the previous paragraph and ethylene waspassed through this catalyst solution for one hour. The polymerrecovered was 1.42 g. of polymer having a melting point of 129-133 C. 1

20 EXAMPLE 9 This example describes the use of a polymeric reactionproduct of methylene dichloride and aluminumto replace the aluminumchloride normally used as an electrolyte. ml. of dichloromethane wascharged to the electrolysis cell and the power supply was turned on at500 volts. Then, 0.3 ml. of a polymeric reaction product of methylenedichloride and aluminum which was made as described in U.S. Pat. No.3,026,310 or 3,018,- 278 containing 0.00465 g. of aluminum was addeddropwise to the electrolysis cell until a current of 0.5 amp wasobtained. Ethylene was bubled through the electrolysis cell all duringthe electrolysis. Electrolysis was continued for 45 minutes and theanode weight loss was 0.0385 g. of aluminum which represents 1.42 millig. atom of aluminum lost. This also represents 1.23 gram atom aluminumloss per faraday with 1.15 millifaradays having been used in theelectrolysis.

The electrolysis solution was added to the polymerization vessel and0.178 g. of dicyclopentadienyl titanium dichloride was added to thevessel. Ethylene was passed through the solution for one hour, thereaction mixture was quenched with methanol, filtered, and thepolyethylene washed on the filter with methanol and dried in a vacuumoven over night. Yield of polymer was 3.53 grams having a melting pointof 129-131 C. This represents 4.97 g. of polyethylene/millimole ofdicyclopentadienyl titanium dichloride.

EXAMPLE 10 Preparation of the pre-electrolysis solution: To a 500 ml.flask is charged 400 ml. of anhydrous dichloromethane and 0.268 g. ofanhydrous aluminum chloride under nitrogen. Maintaining a nitrogenatmosphere the mixture is stirred with a magnetic stirrer and 36milligrams of water is added to the vortex of the stirred liquid. Themixture is stirred over night giving a clear, homogeneous yellowsolution.

Electrolysis: A glass electrolysis cell was set up, equipped with asubsurface gas inlet tube, a magnetic stirring bar and a condenser. Theelectrodes were three weighed concentric hollow aluminum cylinders with0.25 inch separation, the anode being the middle electrode.

The electrolysis cell was flushed with nitrogen and the pre-electrolysissolution added. The pre-electrolysis solution was saturated with dryethylene and the current turned on. The current, 0.5 amp, was suppliedfrom a constant current DC power supply and the voltage required tomaintain this current level was between and volts. During theelectrolysis ethylene was passed through the cell by means of the gasinlet tube. The temperature during electrolysis was 40 C. After 40minutes the electrolysis was stopped and the electrolyzed solutiontransferred to a reservoir on the polymerization reactor. During the 40minute electrolysis 12.44 millifaradays of current were passed. Theelectrodes were removed from the cell, dried and weighed. 0.3389 g. ofthe aluminum anode had been consumed. The loss of aluminum was equal to12.55 mg. atoms and represents 1.01 g. atoms of aluminum lost from theanode per faraday. Aliquots of the clear red solution ofbis-(dichloroaluminum)methane [Cl AlCH AlCl were used forpolymerizations.

EXAMPLE 11 Preparation of the pre-electrolysis solution: To a 500 ml.flask is charged 400 ml. of anhydrous dichloromethane and 0.250 g. ofethyl aluminum dichloride under nitrogen. Maintaining a nitrogenatmosphere the mixture is stirred with a magnetic stirrer and 36milligrams of water is added to the vortex of the stirred liquid. Themixture is stirred over night giving a clear, homogeneous yellowsolution.

Electrolysis: A glass electrolysis cell was set up and equipped with asubsurface gas inlet tube, a magnetic stirring bar and a condenser. Theelectrodes were three weighed concentric hollow aluminum cylinders with0.25 inch separation, the anode being the middle electrode.

The electrolysis cell was flushed with nitrogen and the abovepre-electrolysis solution added. The preelectrolysis solution wassaturated with dry ethylene and the current turned on. The current, 0.5amp, was supplied from a constant current DC power supply and thevoltage required to maintain this current level was between 60 and 80volts. During the electrolysis ethylene was passed through the cell bymeans of the gas inlet tube. The temperature during electrolysis was 40C. After 40 minutes the electrolysis was stopped and the electrolyzedsolution transferred to a reservoir on the polymerization reactor.During the 40 minute electrolysis 12.44 millifaradays of current werepassed. The electrodes were removed from the cell, dried and weighed.0.3196 g. of the aluminum anode had been consumed. The loss of aluminumwas equal to 11.84 milli g. atoms and represents 0.95 g. atoms ofaluminum lost from the anode per faraday. Aliquots of the clear redsolution of bis-(dichloroaluminum)methane [Cl AlCH AlCl were used forpolymerizations.

EXAMPLE 12 This example represents a general method for complexing thecocatalysts for the polymerization of monomers.

A 300 ml. glass vessel equipped with a magnetic stirrer and suitableports for filling, emptying and introduction of inert atmospheres isplaced in the lines after the solvent and electrolysis reservoirs andahead of the reactor. This vessel is referred to as the catalystcomplexer.

The catalyst complexer was charged with 110 ml. of the electrolyzedsolution, containing 2 rnillimoles of Cl AlCI-I A1Cl as prepared inExamples or 11, and 1.9 m1. of a 1.05 -N solution of n-butoxytitaniumtrichloride in dichloromethane was added with a hypodermic syringe. Themixture was stirred for 30 minutes. The complexed catalyst thus preparedis used for polymerizations.

EXAMPLE 13 A two liter stainless steel stirred reactor equipped withsuitable inlet ports, bottom drain, thermocouple, jacket for heating orcooling and a pressure gauge was charged with 500 ml. of dry hexane. Thecomplexed cocatalyst as described in Example 12 was then charged to thereactor with stirring followed by an additional 500 ml. of hexane. Thereactor was sealed and pressured to 120 p.s.i.g. with dry ethylene, andthis pressure was maintained during the entire run. The polymerizationwas exothermic and after 10 minutes the reactor was cooled with air. Thereaction temperature was maintained at 60 (1:2 by control of the amountof cooling air. After 1 hour the reaction mixture was cooled to roomtemperature with water, the reactor vented, flushed with nitrogen andthe reactor emptied. The polymerization mixture was quenched with anequal volume of methanol and filtered under vacuum. The polyethylene waswashed on the filter with additional methanol, slurried in boilingmethanol and refiltered. The polyethylene was vacuum dried on the filterusing a rubber dam and the semi-dried polymer treated with anantioxidant IONOL (2,6-di-tertbutyl-4-methylphenol). The polymer wasthen vacuum dried at 60 C. for 18 hours. The yield as 138.3 g. of solidpolyethylene.

EXAMPLE 14 0.125 g. (0.5 millimole) of dicyclopentadienyltitaniumdichloride-recrystallizedwas dissolved in about one liter ofdichloromethane. The dicyclopentadienyl titanium dichloride solution wastransferred to a reservoir above the polymerization vessel undernitrogen pressure. Then 930 ml. of the titanium compound solution wascharged to the reactor and the stirrer in the reactor was turned on.Between 55 and 60 ml. of the electrolysis solution 22 containing about0.5 millimole of Cl AlCH AlCl was charged to the reactor followed by theremaining 100 ml. of the titanium compound solution. The reactor wassealed and pressure to 82 p.s.i.g. with ethylene. After 25 minutes thepressure was increased to 93 to 95 p.s.i.g. The polymerization wasterminated after one hour, and the reactor was cooled and vented. Afterflushing the reactor with nitrogen the bottom drain of the reactor wasopened and only a trace of polymer was obtained through the drain. Thereactor was pressured with 25 p.s.i.g. of nitrogen and allowed to standover night. The reactor was vented and opened. The walls of the reactorand all the parts were coated with polyethylene. The polymer was removedfrom the reactor and quenched with methanol. The polyethylene wasseparated by filtration from the methanol and washed in a Waring Blendorwith methanol. The polymer was again separated by filtration andslurried in boiling methanol. The polymer was then filtered, washed onthe filter with methanol and sucked dry with vacuum. The polymer wastreated on the filter wtih 10 m1. of IONOL in methanol (one mg. ofIONOL/ ml. methanol). The polymer was dried in the vacuum oven overnight at 60 C. Yield of solid polymer was 57.5 g.

EXAMPLE 15 In this example, the polymerization was carried out underpressure and TiCL; was the heavy metal compound mixed with theelectrolyzed aluminum compound to form the. catalyst. 1 ml. of TiCl /CHCl solution (0.966 N) was added to about 1 liter of dichloromethane. Theclear TiCl /CH Cl solution was charged to a reservoir for use incharging the polymerization vessel. To the polymerization vessel wasadded 900 ml. of the titanium tetrachloride solution followed by 50 ml.of an electrolysis solution containing about 1 millimole of Cl A1CH AlCland the mixture was stirred. Then the remaining 200 ml. of titaniumtetrachloride solution was charged to the reactor and the reactor wassealed. The reactor was then pressurized to 96 p.s.i.g. with ethylene.At about 2 hours and 10 minutes, the pressure was increased to 106p.s.i.g. At about 3 hours, after the beginning of the polymerization,cooling became necessary. At the end of 4 hours, the polymerization wasterminated due to the fact that the ethylene inlet tube became clogged.The reactor was cooled and vented and when it was opened it was found tobe full of polymer. The contents of the reactor were quenched withmethanol, the polymer separated by filtration, slurried in boilingmethanol and filtered again. The polymer was then washed on the filterwith methanol. The polymer was filtered again to remove the methanol.The polymer was then treated with 50 ml. of IONOL solution. The polymerwas then dried overnight in a vacuum at 60 C. Yield of solid polymer was203.3 g.

EXAMPLE 16 This experiment shows the use of n-butoxytitanium trichlorideas the heavy metal compound in a polymerization. 1.25 ml. ofn-butoxytitanium trichloride/methylene dichloride solution (1 millimoleof n-butoxytitanium trichloride) was added to 1 liter ofdichloromethane.

ml. of electrolysis solution was prepared in a similar manner to Example10 or 11. This electrolysis solution had 1.23 rnillimoles ofbis(dichloroalumirrum) methane in it. The reactor was flushed with 45ml. of electrolyzed solution in 500 ml. of dichloromethane and dumped.Then, the 1.25 ml. of n-butoxytitaniurn trichloride/methylene dichloridesolution as described above was charged to methylene dichloride in areservoir above the reactor. The total volume of 1 liter with the addedmethylene dichloride. To the reaction vessel was then charged 800 ml. ofthe n-butoxytitanium trichloride/methylene dichloride solution, then the75ml. of electrolysis solution was added and finally the remaining 200ml. of n-butoxytitanium trichloride/methylene dichloride solution wasadded to the reactor. The reactor was sealed and pressured to 112p.s.i.g. with ethylene. The ethylene was fed over the surface of thereaction mixture and the stirrer speed in the reactor was 1600 r.p.m.Polymerization was continued for 2 hours with no heating or cooling. Thereactor was then cooled to room temperature by water cooling, vented,flushed with nitrogen and the contents of the reactor were dumpedthrough the bottom drain. The reactor was flushed 2 times with 500 ml.of dry methylene dichloride by filling, stirring and dumping. Thereaction mixture was quenched with an equal volume of methanol and thepolyethylene was removed by filtration under vacuum. The polyethylenewas washed on the filter with methanol, slnrried in boiling methanol andseparated again by vacuum filtration. The polyethylene was washed on thefilter with additional methanol and sucked dry with vacuum. Thepolyethylene was then treated with 50 ml. of IONOL solution and wasblended with the polyethylene on the filter with a spatula. Thepolyethylene was then dried overnight in a vacuum oven at 60 C. Yield ofdried polymer was 166.9 grams. This represents 166.9 grams ofpolyethylene/millimoles of n-butoxytitanium trichloride. The polymer hada melting point of 130l34 C.

EXAMPLE 17 This example describes a polymerization wherein the heavymetal compound was ethoxytitanium trichloride and the concentration inthe polymerization vessel was 1 millimole per liter of solvent. 500 ml.of hexane was charged to the polymerization reactor. To the complexerwas added 55 ml. of electrolysis solution containing 1 millimole ofbis-(dichloroaluminum)methane and 0.85 ml. of ethoxytitanium trichloridedissolved in methylene dichloride (1.1195 N, 1 millimole). The mixturein the complexer turned black and then muddy brown. The mixture in thecomplexer was stirred for 30 minutes. Then the contents of the complexerwas charged to the polymerization reactor along with 500 ml. hexane. Thereactor was pressured with ethylene to 120 p.s.i.g. After 30 minutes ofpolymerization, the reaction vessel was heated for 15 minutes to 50 C.Polymerization was continued for one hour after which time the reactorwas cooled and vented, the reaction mixture dumped from the reactor,methanol added to the reaction mixture to quench it, and the polymer wasworked up in the usual manner. Weight of dry solid polymer was 38.4 g.

EXAMPLE 18 This experiment shows that water modified TiCL; is aneffective catalyst whencombined with bis-(dichloroaluminum)methane. Oneliter of dichloromethane which was carefully dried was added to 180microliters millimoles) of water. To this water, methylene dichloridesolu tion was added 14.4 ml. (10 millimoles) of titanium tetrachloridedissolved in hexane (0.696 N TiCl This mixture was refluxed undernitrogen for 2 hours to drive off HCl and cooled under nitrogen. A whiteopaque mixture which did not settle out on standing resulted. Thismixture was transferred to a reservoir over the polymerization reactor.

85 ml. of this water modified TiCl approximately 1 millimole, wascharged to the catalyst complexer and 70 ml. [1 millimole ofbis(dichloroaluminum)methane] of electrolysis solution was added to thetitanium compound. The mixture in the complexer was stirred for minutes.This complexed catalyst was charged to the polymerization reactor withone (1) liter of dry methylene dichloride. The reactor was sealed andpressured to 111 p.s.i.g. with ethylene which had been carefully dried.After about 15 minutes, the reactor was gradually heated with steam andafter about 1 hour and 50 minutes the reactor temperature leveled out at73.5 C. This temperature was maintained by heating with steam. Afterthree hours run time the reactor was cooled, vented and opened. Thereactor was dumped and cleaned out. The reaction mixture was quenchedwith an equal volume of methanol, filtered and 24 washed on the filterwith additional methanol. The solid polyethylene product was dried in avacuum oven at 60 C. over the week-end. The resulting dried polyethyleneproduct was 53.2 g. which represents 53.2 g. of polymer/ millimole oftitanium.

EXAMPLE 19 This experiment shows the use of 0.5 millimole ofnbutoxytitanium trichloride per liter of solution in polymerization.Chemicals: 0.7 ml. of approximately 0.5 millimoles of n-butoxytitaniumtrichloride, 30 ml. [0.5 millimole of bis(dichloroaluminum)methane]electrolysis solution, 1 liter of dichloromethane which had beencarefully dried as were the other materials and carefully driedethylene. The n-butoxytitanium trichloride/methylene dichloride wascharged to 500 ml. of methylene dichloride in a reservoir and anadditional 500 ml. of methylene dichloride was added. 800 ml. of thistitanium compound solution was charged to the reactor followed by theelectrolysis solution and finally the remaining 200 ml. of the titaniumcompound solution. The reactor was sealed and pressured to 72 p.s.i.g.with ethylene. Polymerization temperature was 62 C. and polymerizationtimes was 2 hours. The reactor was dumped through the bottom drain andthe reaction mixture quenched with an equal volume of methanol. Thesolid polyethylene product was filtered 01f under vacuum and washed onthe filter with methanol. The polyethylene was slnrried with boilingmethanol, filtered, washed on the filter with methanol and sucked dryunder vacuum. The polyethylene was then dried in a vacuum oven overnight at 60 C. Yield of solid polymer was 10.6 g.

EXAMPLE 20 This is another run at an n-butoxytitanium trichloride levelof 1 millimole per liter of solvent. The polymerization reactor wascharged 500 ml. of hexane. To the complexer was added 52 ml. of bis-(dichloroaluminum) methane solution (1 millimole) and 0.995 ml. ofn-butoxytitanium trichloride solution (1 millimole). The mixture wascomplexed for 5 minutes and the brownish-black solution mixtureresulted. The catalyst was added to the reactor and then an additional500 ml. of hexane was added to the reactor. The reactor was pressured to116 p.s.i.g. with ethylene. The temperature was allowed to rise of itsown accord, and reached 57 C. in one hour. The reactor was then cooled,vented and to the reactor was added 500 ml. of hexane before dumping thecontents of the reactor. The reactor was washed with two 500 ml.portions of hexane. The polymer was quenched with methanol, filtered,washed and boiled for about /2 hour with methanol. The polymer was thenfiltered from the methanol and a vacuum pulled on the polymer on thefilter. Then to the polymer there was added 25 ml. of IONOL solution,and this was mixed in with the polymer. The polymer was dried over nightin a vacuum oven at 65 C. Solid polymer yield was 93.7 g.

EXAMPLE 21 This experiment represents a 2 millimole concentration ofn-butoxytitanium trichloride in hexane polymerization run. To thereactor was added 500 ml. of hexane. To the complexer was added ml. ofbis-(dichloroaluminum) methane solution (2 millimoles) and 1.9 ml. ofn-butoxytitanium trichloride solution (2 millimoles). The complexer wasrun for 5 minutes and then the complexed catalyst was added to thereactor along with an additional 500 ml. of hexane. The reactor waspressured to 116 p.s.i.g. with ethylene. The reaction was very fast andtemperature control was essentially lost after 5 minutes. After one hourthe reactor was vented and 1 liter of hexane was added to the reactor.On dumping the reactor approximately 1 liter of hexane was recovered.The reactor was opened and was found to be full of polymer. The polymerwas scraped out of the reactor and washed and boiled with methanol. Themethanol was filtered from the polymer and 50 ml. of

IONOL solution was added to the filter cake. The polymer was dried in avacuum oven over night at 65 C. and the yield of solid polyethylene was198.5 grams.

EXAMPLE 22 This is another run using equal molar amounts of his-(dichloro-aluminum)methane and n-butoxytitanium trichloride at a 1millimole level of each in the polymerization medium. To the reactor wascharged 500 ml. of hexane. To the complexer was added approximately 50ml. of bis-(dichloro-aluminum)methane solution (1 millimole) dissolvedin methylene dichloride and 0.95 ml. of n-butoxytitanium trichloridesolution (1 millimole) dissolved in methylene dichloride. The complexerwas run for minutes to mix the catalyst and a chocolate brown solutionresulted. The catalyst was added to the reactor and an additional 500ml. of hexane was added to the polymerization reactor. The reactor wasclosed and pressured to 116 p.s.i.g. with ethylene. The temperatures inthe reactor rose steadily throughout the one hour polymerization run. Atthe end of the hour, the reactor was cooled and vented. The reactor wasthen opened. The reaction mixture in the reactor was quenched withmethanol and transferred to a beaker where it was left standing overnight. The next day the polymer was worked up in the usual fashionincluding the addition of the normal amount of IONOL antioxidant to thepolymer. Dried solid polymer weight 172.5 g.

EXAMPLE 23 In this example, the electrolyte was tetraethylammoniumchloride rather than aluminum chloride. The preelectrolysis solutionconsisted of 400 ml. of dichloromethane and 0.12 g. of (C Ht -J NCI.During the electrolysis 6.895 milligram atoms of aluminum was lost fromthe anode. This represents 0.60 gram atoms of aluminum lost per faradayused. Electrolysis time was 37 minutes and during this time a constantcurrent of about 0.5 amp was maintained. Ethylene blanketing was usedduring the electrolysis. During the electrolysis 11.51 millifaradays ofelectricity were used.

To the polymerization reactor was added 500 ml. of hexane. To thecomplexer was charged 130 ml. of the electrolyzed solution having 2millimoles of bis-(dichloro-aluminum)methane therein and 1.9 ml. (2millimoles) of n-butoxytitanium trichloride solution. The mixture ofcatalyst components was stirred for five minutes in a complexer and thencharged to the reactor. An additional 500 ml. of hexane was charged tothe reactor. The reactor was then pressured to 116 p.s.i.g. withethylene. The temperature in the reactor rose slightly and then thereactor was heated with steam. After one hour the reactor was vented anddumped. The product was quenched with methanol and worked up in theusual manner. Yield of recovered solid polyethylene was 8.8 grams.

EXAMPLE 24 This example shows a polymerization run in which the ratio oftitanium compound to aluminum compound was 2:1 molar. To thepolymerization vessel was charged 500 ml. of hexane. To the complexerwas added 100 ml. of electrolysis solution containing 1.54 millimoles ofbis- (dichloro-aluminum)methane and 2 ml. of mbutoxytitanium trichloridesolution containing 3.08 millimoles of titanium compound. The complexerwas run for 30 minutes to mix the catalyst components and then thecatalyst was added to the reactor. After the addition of the caalyst tothe reactor 500 ml. of hexane was added and the reactor was pressured to118 p.s.i.g. with ethylene. At the end of an hour the reactor was cooledto C. vented and dumped. The reactor was washed out with two 500 ml.portions of hexane. The reaction mixture was then quenched with methanoland let stand. The quenched reaction mixture was worked up in the usualmanner to purify and recover the solid polymer product. 90.0 g. of solidpolyethylene were recovered.

26 EXAMPLE 25 This experiment shows a ratio of the titanium compound toaluminum compound of 1:2 molar. To the polymerization reactor wascharged 500 ml. of hexane. To the complexer was added 130 ml. ofbis-(dichloro-aluminum) methane solution having 2 millimoles of thealuminum compound therein. Also added to the complexer was 0.95 ml. ofn-butoxytitanium trichloride s0- lution having 1 millimole of thetitanium compound therein. The complexer was run for 30 minutes afterwhich time the catalyst was added to the polymerization reactor alongwith another 500 ml. of hexane. The reactor was pressured to 117p.s.i.g. with ethylene. The uptake of the ethylene appeared to be slow.At the end of one hour the reactor was vented and dumped and the polymerworked up in the usual fashion. Yield of solid polyethylene polymer was10.1 g.

EXAMPLE 26 This example describes a normal electrolysis and a use of themother liquor from the polymerization for another polymerization. In theelectrolysis, ethylene blanketing was used and the anode loss was 2.97millimoles of aluminum. To the electrolyzed solution was added 0.5 g. ofdicyclopentadienyltitanium dichloride and ethylene was passed throughthe catalyst mixture for one hour. After the hour of polymerization, thepolymer was separated by filtration in a closed-fritted filter and thepolymer was washed two times with 10 cc. portions of methylenedichloride. The mother liquor from the filtrations and the washings werefed to a tubular reactor under nitrogen blanketing and ethylene wasbubbled through the stirred mixture for one hour. Methanol was added tothe reaction mixture and the polymer was separated by filtration. Thepolymer products from both the first and second polymerizations wereseparately washed with methanol, then, slurried with hot methanolcontaining 5% concentrated hydrochloric acid. The polymers were thenfiltered from the methanol and HCl, were washed and dried in a vacuumoven at about 60 C. The weight of polymer from the first polymerizationwas 3.48 grams and it had a specific viscosity of 0.043 at 0.1%concentration in xylene at 105 C. The yield of polymer from the secondpolymerization was 1. 69 g. and its specific viscosity was 0.074 at 0.1%concentration in xylene and at 105 C.

EXAMPLE 27 This example shows a polymerization usingtetra-nbutoxytitanium as the heavy metal compound. To the complexer wascharged 235 ml. of bis-(dichloro-aluminum)methane having 4 millimoles ofBDCAM therein and 0.35 ml. of tetram-butoxytitanium (1 millimole) andthe mixture was stirred for 15 minutes. The titanium compound Waspurchased. The contents of the complexer were then charged to apolymerization reactor along with one liter of methylene dichloride. Thereactor was pressured to 104 p.s.i.g. with ethylene, and after a shortperiod the reactor was vented to p.s.i.g. and heated to 75 C. Theethylene pressure was maintained at 90 p.s.i.g. during the balance ofthe run which Was one hour of polymerization. At the end of the hour thereactor was cooled, vented and the polymer recovered and worked up inthe usual manner. Yield of polymer was 11.5 g.

EXAMPLE 28 This example describes a polymerization in which the :heavymetal compound was n-dodecyloxytitanium trichloride at a 2 millimolelevel in solvent. The titanium compound was prepared in dichloromethanesolvent and used without isolation for the later polymerization. Thetitanium compound was prepared by charging methylene dichloride andtitanium tetrachloride to a reaction vessel. Then to the reaction vesseln-dodecyl alcohol was added drop-wise until an equal molar amount hadbeen added based on the titanium tetrachloride. The reaction mixture wasthen refluxed for 8 hours at which time no further hydrogen chloride wasbeing evolved. The product solution of n-dodecyloxytitanium trichloridein methylene dichloride contained 1 millimole of the titanium compoundper 1.1 ml. of solution.

To the polymerization reactor was charged 500 ml. of methylenedichloride. To the complexer was charged 60 ml. ofbis-(dichloroaluminum)methane (2 millimoles) and 2.2 ml. of then-dodecyloxytitanium trichloride (2 millimoles) and the mixture in thecomplexer was stirred for 5 minutes. Along with an additional 500 ml. ofmethylene dichloride, the contents of the complexer were charged to thepolymerization vessel and the polymerization vessel was pressured withethylene to 102 p.s.i.g. The reaction was exothermic and the temperaturerose quickly to 75 C. and was maintained between 75 and 80 C. with aircooling of the reactor. After minutes of polymerization the ethylenefeed was turned off and the reactor was cooled, vented, 500 ml. ofmethylene dichloride was added and the contents of the reactor dumped.The reactor was washed once with 500 ml. of methylene dichloride. Mostof the mother liquor was siphoned from the polymer. Then the polymer waswashed twice with methanol and boiled for 30 minutes with methanol. Thepolymer was recovered by filtration, was washed and after the removal ofthe methanol, 40 ml. of IONOL solution was added and blended intopolymer. The polymer was dried in a vacuum oven. Yield of dried polymerwas 134 g.

EXAMPLE 29 This example illustrates the making of a copolymer ofethylene/l-butene (97/3 molar ratio) using a catalyst of the invention.To the polymerization reactor was charged 500 m1. of methylenedichloride and to the complexer was added ml. of methylene dichloride,30 ml. of bis(dichloroaluminum)methane (1 millimole) and 1.1 ml. ofn-dodecyloxytitanium trichloride solution (1 millimole). The complexercontents were stirred for 5 minutes and then the contents of thecomplexer were added to the reactor along with 480 ml. of methylenedichloride. The reactor was pressured to 86 p.s.i.g. using anethylene/l-butene comonomer mixture. The reaction was exothermic and thetemperature steadily rose to about 66 C. At the end of one hour ofpolymerization the reactor was cooled, vented and the contents of thereactor dumped. The reactor was then opened and it was found thatpolymer was caked on the walls. The polymer was removed from the reactorand worked up in the normal manner. Yield of polymer was 39.1 g.

EXAMPLE 30 This example illustrates the use of di-n-butoxytitaniumdichloride in a polymerization. The titanium compound is made by adding164.4 g. of dichloromethane and 22.2 g. (0.117 mole) of titaniumtetrachloride was charged to a reactor and over a 15 minute period, 38.8g. (0.114 mole) of tetra-n-butyltitanate was added drop-wise to thetitanium tetrachloride in dichloromethane at ice water temperature. Thismixture was stirred at room temperature for four days. The final weightof solution was 223.0 grams having a density of 1.28 g./ml. Thissolution then is 1.328 normal or has 1 millimole of di-n-butoxytitaniumdichloride per 0.755 ml. of solution.

To the polymerization reactor was added 500 ml. of methylene dichlorideand to the complexer was added 52 ml. of bis(dichloroaluminum)methane (1millimole) and 0.75 ml. of di-n-butoxytitanium dichloride (1 millimole).The mixture in the complexer was stirred for 5 minutes and then added tothe reactor along with an additional 500 ml. of methylene dichloride.The reactor was pressured to 106 p.s.i.g. with ethylene and thetemperature rose gradually to 67 C. After one hour of polymerization thereactor was cooled, vented and the contents dumped.

28 The reactor was washed out with 1 liter of methylene dichloride andthe washings were combined with the crude product. The product wasworked up in the usual manner and 62.9 g. of fibrous polymer wasrecovered.

EXAMPLE 31 This example describes the use of n-dodecylthiotitaniumtrichloride for polymerization at the 2 millimole level in solvent. Then-dodecylthiotitanium trichloride was prepared in a similar manner tothe n-dodecyloxytitanium trichloride using a slight excess over an equalmolar amount of l-dodecanethiol to titanium tetrachloride. The reactionmixture was refluxed overnight and still some hydrogen chloride wasbeing given off. Also the flask contained some solids and additionalmethylene dichloride was added. The solution was still not complete.Density of the solution was 1.315 g./ml. The solution calculated to be0.456 normal having 1 millimole of n-dodecylthiotitanium trichloride per2.19 ml. of solution.

To the polymerization reactor was added 500 ml. of methylene dichlorideand to the complexer 105 ml. of bis(dichloroaluminum) methane (2millimoles) and 4.4 ml. of n-dodecylthiotitanium trichloride (2millimoles). The mixture in the complexer was stirred for 5 minutes andwas then charged to the reactor along with an additional 500 ml. ofmethylene dichloride. The reactor was pressured to 102 p.s.i.g. withethylene and the temperature in the reactor gradually rose to 73 C.during the polymerization. Polymerization time was one hour after whichtime the reactor was cooled and 500 ml. of methylene dichloride wasadded and mixed with the reactor content before discharging the reactor.The polymer prodnot was worked up and recovered in the usual manner.Yield of polymer product was 135.5 g.

EXAMPLE 3 2 This example illustrates the use of n-hexadecyloxytitaniumtrichloride as a catalyst in polymerization at a 1 millimole level insolvent. The titanium component was made in an analogous method to themaking of the n-dodecyloxytitanium trichloride except that the mixtureof titanium tetrachloride and hexadecyl alcohol was stirred for 4 daysand then refluxed for 18 hours. At the end of this time hydrogenchloride evolution had ceased. The weight of the contents of the flaskwas 168.3 g. and the density of this solution was 1.25 g./ ml. Thesolution was 0.845 normal and 1 millimole of n-hexadecyloxytitaniumtrichloride was contained in 1.18 ml. of solution.

To the reactor was charged 500 ml. of dichloromethane and to thecomplexer 55 ml. (1 millimole) of his (dichloroaluminum)meth'ane and 1.2ml. (1 millimole) of n-hexa decyloxytitanium trichloride. The complexercontents were stirred for 5 minutes and then charged to the reactorfollowed by the addition of 500 ml. of dichloromethane. The reactor waspressured to 102 p.s.i.g. with ethylene. The temperature in the reactorrose steadily to 56 C. and after one hour of polymerization the reactorwas cooled, vented and dumped. Then the reactor was rinsed with 500 ml.of dichloromethane. The product was worked up and recovered in the usualmanner and 99.0 g. of product was the yield.

EXAMPLE 33 This example shows a polymerization usingtri-n-butoxytitanium chloride as a catalyst component at a 2 millimolelevel in solvent. 65.2 g. of dichloromethane was added to a ml. flaskunder nitrogen blanketing and the tri-nbutoxytitanium chloride was madeby adding tetra-nbutoxytitanium to titanium tetrachloride at ice-bathtemperature and refluxing to insure complete reaction. The desiredproduct tri-n-butoxytitanium chloride was then recovered and purifiedafter removing the solvent by distillation of the reaction mixture. Forpolymerization a solution was made by dissolving 7.2 g. (0.0238 mole) oftri-n-butoxytitanium chloride in 65.2 g. of dichloromethane. Thesolution was 0.437 normal and 1 millimole dichloride. Complexing timewas minutes, polymerization pressure 75 p.s.i.g. and run time 30minutes. Temperature increased from 24-40 C. and water cooling was usedon the reactor for the first 2 /2 minutes. Recovered and ethylene shownin the following table. The reactor was then pressured to 80 p.si.g.with this hydrogen/ ethylene mixture without stirring. The stirrer wasthen turned on in the reactor and pure ethylene feed was polymer was24.1 g. of solid polyethylene. 5 introduced into the reactor at 80p.s.i.g. Polymerizations were continued until no more ethylene wasabsorbed. EXAMPLE 40 Solvent charged to the reactor was 1.5 liters. Thebis(di- This example describes the use of manganeseacetylchloroaluminum)methane used in the runs summarized acetonate inthe presence of hydrogen as a catalyst combelow was madeelectrolytically in the usual fashion. The ponent in polymerization. Theusual amounts of methylruns are summarized in the following table:

TABLE I Grams Milli- Milli- 1 polymer] Grams moles, moles, Mole per-Grams rnM polymer] Run number BDCAM V0013 Solvent cent, H2 polymer V0013V0013 I28 I 6 I /I2 1.0 -11 45.1 4,510 26,100 0.021 0. 48 22.8 1.0 1787.5 3,750 21,600 0. 008 1.05 15.5 1.0 17 39.4 3,910 22, 750 0.175 2. 7515.5 d 1.0 17 69.6 6,960 40, 000 as 38.8 10.2

1 BD CAM=bis(dichloroaluminurmmethane; 2 111M=millimole.

6 Reactor cleaned prior to this run.

ene dichloride solvent were used in the reactor. The charge to thecomplexer was 0.65 ml. manganese acetylacetonate (0.05 millimole) inmethylene dichloride and 65 ml. bis(dichloroaluminum)methane (0.5millimole) in methylene dichloride. Complexer time was 5 minutes andpolymerization run time 1 hour, during which the temperature rose from24.533 C. After the catalyst was charged to the complexer, the reactorwas flushed 5 times with high purity hydrogen and then pressured top.s.i.g. with hydrogen, and then the reactor was pressured to 73p.s.i.g. with ethylene. Polymer was worked up in the usual fashion andthe yield was 12.6 g. of solid polyethylene, 252 g. of polymer/millimoleof manganese acetylacetonate.

If the hydrogen treatment described in these examples is not used, themelt indexes will normally be less than 0.01 I

EXAMPLE 43 TABLE I1 Milli- Milli- Milli- Milli- Reaction Reaction GramsRun moles, moles, moles, moles, time, 6011113., poly- H20 Modifiermodifier minutes C. mer Remarks 10 23-75 Solid polymer made. 10 23-74D0. 20 23-63 36.7 10 2370 70.6 10 23-80 65.5 10 25-63 47.0 30 24-78 74.1

1 BDCAM=bis(dichloroalu1ninum)methane. 3 P=tripheny1phosphine.

EXAMPLE 41 EXAMPLE 44 This example describes the use of cobaltacetylacetonate EXAMPLE 42 The series of runs described in this exampleshow that i the melt index of polyethylene using abis(dichloroaluminum)methane/VOCl catalyst can be controlled byhydrogen. All runs were made at 80 p.s.i.g. with the polymerizationbeing started at room temperature and controlled at 77 C. with heatbeing supplied from an oil bath or cooling from water. Ethylene andhydrogen were premixed in a surge tank to give the ratio of hydrogenThis example describes the preparation by electrolysis of a solution ofhis(dichloroaluminum)methane and an analysis of the solution. To a glasselectrolysis cell Was added 564.4 g. of pre-electrolysis solutionprepared as in 5 Example 10 or 11 containing 5 millirnoles of Cl AlOI-Iper liter of solution with 2.88 C1-/Al. ratio. The solution wassaturated with ethylene and electrolyzed for 40 minutes at 0.5 amp. withsteady state voltage of -195 volts. Ethylene was continuously bubbledthrough the cell during electrolysis. After electrolysis was complete,the bis(dichloroaluminum)methane solution was transferred to a 500 ml.flask under nitrogen. The mixture was refluxed for about 30 minutes todrive off excess ethylene and any HCl if present. During electrolysis12.21 millifarads of current were passed and 0.3377 g. (12.51 milli g.atom) of aluminum was lost from the anode. This corresponds to 1.03 g.atom of Al/F. The weight of these cathodes remained unchanged. Weightfractions of the solution were analyzed for Cl, Al-C bonds and Al.

Analysis.Calcd for A1 CH Cl Al, 0.10%; AlC bonds, 12.51milliequivalents; Cl-, 30.75 milliequivalents. Found: Al, 0.09%; Al-Cbonds, 12.01, 11.77 millieqnivalents; Cl, 30.00, 30.00 milliequivalents.The Al and Cl analyses include the Cl AlOH electrolyte in the solution.The structure of --AlCH Al was established by decomoftri-n-butoxytitanium chloride is contained in 2.29 ml. of solution.

To the reactor was added 500 ml. of dichloromethane and to the complexer105 ml. of bis(dichloroaluminum) methane (2 millimoles) and 4.6 m1. (2millimoles) of trin-botuxytitanium chloride. The complexer was stirredfor minutes and then the contents of the complexer were charged to thereactor followed by an additional 500 ml. of dichloromethane. Thereactor was pressured to 104 p.s.i.g. with ethylene. The temperaturerise was slow but increased after 30 minutes. At the end of 90 minutesthe reactor was cooled, vented and dumped. The polymer was worked up andrecovered in the usual manner. Yield of polymer was 27.5 g.

EXAMPLE 34 This example describes the use of n-hexadecyl amine titaniumtetrachloride addition complex as a catalyst component in polymerizationat the 2 millimole level in solvent. The titanium specie was made byadding an equal molar amount of hexadecylamine to titanium tetrachloridein dichloromethane and after mixing to dissolve all components themixture was refluxed for 24 hours. The product solution was 0.749 normaland 1 millimole of n-hexadecylamine titanium tetrachloride was containedin 1.33 ml. of solution.

To the reactor was charged 500 ml. of dichloromethane and to thecomplexer 110 ml. (2 millimole) of bis(dichloroaluminum)methane and 2.7ml. (2 millimole) of n-heXadecylaminotitanium trichloride. The mixturein the complexer was stirred for 5 minutes and then charged to thepolymerization reactor. An additional 500 ml. of dichloromethane wasadded to the reactor and the polymerization was carried out for onehour. At the end of the one hour of polymerization the reactor wascooled, vented and dumped. The ethylene polymer was worked up andrecovered in the usual manner and the yield of polymer was 86.0 g.

EXAMPLE 35 This example describes the use of H ll Cr(CHaCCHC C alachromium acetylacetonate as a catalyst component in polymerization. Tothe reactor was charged 500 ml. of methylene dichloride and to thecomplexer was charged 75 ml. of bis(dichloroalminum)methane (BDCAM) (0.6millimole) dissolved in methylene dichloride and made in the usualmanner and 1.6 ml.

(0.06 millimoles) in methylene dichloride. The mixture in the complexerwas stirred 5 minutes and then added to the reactor. An additional 500ml. of methylene dichloride was added to the reactor and the reactor waspressured to 75 p.s.i.g. with ethylene. Polymerization was carried onfor 30 minutes after which time the reactor was vented and dumped. Thereactor was then washed with 500 ml. of methylene dichloride and thewashings were added to the polymer. The mixture of the polymer with thewashings was quenched with methanol and 5.2 g. of dried solidpolyethylene product was recovered.

EXAMPLE 3 6 This example describes the use of II ll Fe (CH O CHCCHmferric acetylacetonate as a polymerization catalyst component. 500 ml.of methylene dichloride was charged to the reactor and to the complexerwas charged 125 ml. of

(1.0 millimole) and H II Fe(CH CCHCCHa)a (0.1 millimole) in methylenedichloride. The mixture in the complexer was stirred for 5 minutes andthen added to the reactor. An additional 500 ml. of methylene dichloridewas added to the reactor and the reactor was pressured to 75 p.s.i.g.with ethylene. Polymerization was carried on for 30 minutes after whichtime the reactor was vented and dumped. The polymer was very finelydispersed in the reaction medium. The reactor was washed with 500 ml. ofmethylene dichloride and the wash was added to the polymer suspension.The mixture was quenched with methanol and 8.0 g. of solid drie'dpolyethylene was recovered.

EXAMPLE 37 This example describes the use of the o V(CHa OH( JCHs)avanadium acetylacetonate as a catalyst component in polymerization. Tothe reactor was charged 500 ml. of methylene dichloride and to thecomplexer 70 ml. of bis- (dichloroaluminum)methane (1.0 millimole) inmethylene dichloride and 1 ml. of vanadium acetylacetonate (0.056millimole) in methylene dichloride. The mixture in the complexer wasstirred 5 minutes and then added to the reactor along with an additional500 ml. of methylene dichloride. The reactor was pressured to 75p.s.i.g. with ethylene for 5 minutes after which time the ethylene wasshut off and the reactor cooled. The reactor was opened to removepolymer. The polymer was worked up and dried in the usual fashion.Weight of polymer was 75.2 g.

EXAMPLE 3 8 This example describes the use of manganese acetylacetonateas a catalyst component in polymerization. Manganese acetylacetonate wasnot as soluble as were some of the other metal acetylacetonates and apartial solution slurry of manganese acetylacetonate was prepared byadding 2,550 g. of manganese acetylactonate to 1.33 ml. ofdichloromethane and stirring overnight. The polymerization was conductedin a similar fashion to Example 37. To the complexer was charged 1.3 ml.of manganese acetylacetonate (0.1 millimole) in methylene dichloride and111 ml. of bis(dichloroaluminum)methane (1 millimole) in methylenedichloride. The usual amount of methylene dichloride was added to thereactor as in the previous experiment. Time of the catalyst componentsin the complexer was 5 minutes and a homogeneous solution resulted. Thereactor was pressured to 75 p.s.i.g. with ethylene and thepolymerization run for 10 minutes. Temperature rose from 2376 C. Therecovered polymer was worked up in the usual manner and the yield was54.8 g. of solid polyethylene, 548 g. per millimole of manganeseacetylacetonate.

EXAMPLE 39 This example describes the use of nickel acetylacetonate[Ni(CHa( lCH(iJCHa)2l in conjunction with VOCl as catalyst components inpolymerization. This experiment was run in a similar manner to Example37 with like amounts of solvent being used. The charge to the complexerwas 30 ml. of bis(dichloroaluminum)methane (0.2 millimole), 1 ml. ofVOCI (5 X 10- mole) in methylene dichloride and 1 m1. of nickelacetylacetonate (5x10 mole) in methylene position of thebis(dichlorosluminum)methane solution with CH OD to give H CD Thealuminum carbon bonds were analyzed by the method of S. A. Bartkiewiczand J. W. Robinson, Anal. Chim. Acta., 20, 326 (1959), with solvent forthe iodine being dichloromethane rather than benzene.

EXAMPLE 45 This example describes the polymerization of vinyl chlorideusing a bis(dichloroaluminum)methane and dodecyloxytitanium trichloridecatalyst. To the polymerization vessel was added 45 ml.bis(dichloroaluminum) methane solution in methylene dichloride (lmillimole of the aluminum compound) and 3.2 ml. of dodecyloxytitaniumtrichloride (1 millimole in methylene dichloride). Then 25 ml. of vinylchloride was added to the polymerization vessel. The molar ratio oftitanium compound to aluminum compound is 1:1. After five hours,methanol was added to the reaction mixture which was stripped to removesolvent. The residue, after the solvent removal, was washed with hexaneleaving a solid polymer. An infra-red examination of the sample of thispolymer indicated that it was similar to polyvinyl chloride (film). Thesoftening point of the polymer was around 90 C.

EXAMPLE 46 This example describes the polymerization of ethylene usingmolybdenum acetyl acetonate,

as the heavy metal component of the catalyst. T o the reactor wascharged 500 ml. of hexane. To the complexer was charged 70 ml. ofbis(dichloroaluminum)methane (2 millimoles) and 0.118 g. of molybdenumacetyl acetonate with ml. of hexane. The mixture of catalyst componentswas stirred together for five minutes then charged to the reactor. Anadditional 500 ml. of hexane was charged to the reactor and the reactorwas pressured to 70 p.s.i.g. with ethylene. Polymerization run time was/2 hour after which time the reactor was cooled, vented and the contentsdumped. From the reaction mixture was recovered 2.4 g. of solidpolyethylene and 10.8 g. of liquid oily polyethylene.

EXAMPLE 47 This example describes the polymerization of ethylene usingtitanyl acetyl acetonate as the heavy metal component of the catalyst.To the reactor was charged 500 ml. of hexane and to the complexer wascharged 100 ml. of bis(dichloroaluminum)methane (2 millimoles) and 2.5ml. (0.2 millimole) of titanyl acetyl acetonate. After five minutes ofcomplexing, the catalyst mixture was added to the polymerization vesseland 500 ml. of additional hexane was added to the polymerization vessel.The reactor was pressured to 70' p.s.i.g. with ethylene andpolymerization was continued for one hour after which time the reactorwas cooled, vented and dumped. The product was worked up and recoveredin the usual manner. The product was 5.2 g. of solid polyethylene plus atrace of oily or liquid polyethylene.

EXAMPLE 48 This example describes the use of cobalt acetyl acetonate inthe polymerization of ethylene. To the reactor was charged 500 ml. ofhexane and to the complexer was charged 90 ml. (2 millimoles ofbis(dichloroaluminum) methane and 4 ml. (0.2 millimole) of cobalt acetylacetonate O O CMCHa C'H CH3);

The catalyst mixture was stirred in the complexer for five minutes andthen charged to the reactor. An additional 34 500 ml. of hexane was alsocharged to the reactor. The reactor was pressured to 70 p.s.i.g. withethylene and the polymerization was allowed to continue for one hour.After the hour of polymerization, the reactor was cooled, vented and thereaction mixture dumped. The reaction mixture was worked up and thepolymer recovered in the usual fashion. Yield of polymer was 10.6 g. ofsolid polyethylene.

EXAMPLE 49 This example describes the polymerization of ethylene usingzirconium acetyl acetonate dumped. The reaction mixture was worked up inthe usual fashion and the product recovered. Yield of solid polyethylenewas 38.6 g.

EXAMPLE 50 This example describes the use of nickel acetyl acetonate asthe heavy metal component of the catalyst. To the reactor was charged500 m1. of hexane and to the complexer 75 ml. (2 millimoles) ofbis(dichloroaluminum) methane and 0.051 g. (0.2 millimole) of nickelacetyl acetonate. The catalyst components in the complexer were stirredfor five minutes and then added to the reactor. Also added to thereactor was 500 additional m1. of hexane. The reactor was pressured to72 p.s.i.g. with ethylene. The temperature in the reactor rose steadilyto 70 C. due to the exothermic heat of polymerization. At 30- minutes,uptake of oxygen was still good but the reactor was cooled, vented andthe reaction mixture dumped. The reactor was washed with 300 ml. ofhexane. No solids were found in the reaction mixture. The reactionmixture, a solution, was shaken first with water containing a little HCland then with two separate portions of distilled water. The organicproduct layer was dried overnight over magnesium sulfate. The driedsolution was filtered from the magnesium sulfate and distilled toseparate the product into five liquid fractions plus a residue fractionwhich was distilled at reduced pressure. Analysis of these fractionsindicated that compounds had been made having from 4 to 20 carbon atoms.Weight of the 7 fractions, including the residue, amounted to 35.4 g.The extra liquid fraction was from the distillation under vacuum of theresidue.

Although the invention has been described in terms of specifiedembodiments which are set forth in considerable detail, it should beunderstood that this is by way of illustration only and that theinvention is not limited thereto since alternative embodiments andoperating techniques will become apparent to those skilled in the art inview of the disclosure. Accordingly, modifications are contemplatedwhich can be made without departing from the spirit of the describedinvention.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A catalyst useful for polymerization consisting essentially of amixture of (1) a compound of the formula X MCH MX wherein M is boron, aGroup II or IIIA metal of the Periodic Table, X is a halogen atom. and nis one less than the valence of M and (2) a compound of a transitionmetal of Groups III-B, IV-B, V-B, VI-B, VII-B, VIII or I-B of thePeriodic Table in proportions such that the molar ratio of compound (1)to compound (2) lies in the range from about 0.3 :1 to about 200:1.

2. A catalyst of claim 1 to which has been added an electron donatingcompound in sufficient amount to modify the catalyst activity butinsufficient to kill the catalyst activity.

3. A catalyst of claim 2 wherein the electron donating compound is waterin an amount from about 0.01 to about 2.0 moles per mole of compound(1).

4. A catalyst of claim 1 wherein (l) is Cl AICI-I AICI and (2) is acompound having an electron donating group.

5. A catalyst of claim 1 wherein (l) is Cl AlOH AICI and (2) isdicyclopentadienyltitanium dichloride.

6. A catalyst of claim 1 wherein (1) is Cl A1CH AlCl and (2) iscyclopentadienyltitanium trichloride.

7. A catalyst of claim 1 wherein (1) is Cl AlOH AlCl and (2) is titaniumtetrachloride.

8. A catalyst of claim 7 to which has been added an electron donatingcompound in suflicient amount to modify the catalyst activity butinsufiicient to kill the catalyst activity.

9. A catalyst of claim 8 wherein the electron donating compound is waterin an amount from about 0.01 to about 2.0 moles per mole of Cl AlCH AlCl10. A catalyst of claim 1 wherein (1) is Cl AlCH AlCl and (2) isdicyclopentadienylvanadium dichloride.

11. A catalyst of claim 1 wherein (1) is Cl AlCH AlCl and (2) isvanadium oxychloride.

12. A catalyst of claim 11 to which has been added an electron donatingcompound in sufiicient amount to modify the catalyst activity butinsufficient to kill the catalyst activity.

'13. A catalyst of claim 12 wherein the electron donating compound iswater in an amount from about 0.01 to about 2.0 moles per mole of CIAICH AlCI 14. A catalyst of claim 1 comprising a mixture of (1) CI AICHAICI and CI AICH AlClCH AICI and (2) is vanadium oxychloride.

15. A catalyst of claim 1 wherein (1) is Cl AlCH AlCl and (2) istitanium tetraiodide.

16. A catalyst of claim 15 wherein an amount of water from about 0.01 toabout 2.0 moles per mole of Cl AlcH AlCl has been added to modify thecatalyst activity.

17. A catalyst of claim 1 wherein (1) is Cl AlCH AlCl and (2) is acompound of the formula (R Z),,,TiX' wherein R is a hydrogen atom or ahydrocarbon group, m is an integer from 1 to 4, X is a halogen atom andZ is O, S, Se, Te or NR where R is defined in the same manner as R.

18. A catalyst of claim 1 wherein (1) is Cl AlCH AlCl and (2) is acompound of the formula (R D)-TiX' wherein R is a hydrogen atom or ahydrocarbon group, X is a halogen atom and D is selected from the groupconsisting of nitrogen, phosphorus, arsenic, antimony and bismuth atoms,and oxides and sulfides of phosphorus, arsenic and antimony.

19. A catalyst of claim 17 wherein R is an alkyl group having from 4 to20 carbon atoms, X is a chlorine atom, and Z is O.

20. A catalyst of claim 19 wherein R is an n-butyl group.

21. A catalyst of claim 17 wherein R is an alkyl group having from 4 to20 carbon atoms, m. is 1, X is a chlorine atom and Z is S.

22. A catalyst of claim 17 wherein R is an alkyl group having from 4 to20 carbon atoms, m is 1, X is a chlorine atom and Z is NH.

23. A catalyst of claim 1 wherein (1) is and (2) is vanadiumacetylacetonate.

24. A catalyst of claim 1 wherein (1) is CI AICH AICI and (2) vanadiumtetrachloride.

25. A catalyst of claim 1 wherein (1) is CI AIOH AICI and (2) vanadylacetylacetonate.

26. A catalyst of claim 1 wherein (1) ,is Cl AlCH A1Cl and (2) manganeseacetylacetonate.

27. A catalyst of claim 1 wherein (l) is Cl AloH AlCl and (2) ironacetylacetonate.

28. A catalyst of claim 1 wherein l) is Cl AlCH AlCl and (2) cobaltacetylacetonate.

29. A catalyst of claim 1 wherein (1) is Cl AlCH AlCl and (2) chromiumacetylacetonate.

30. A catalyst of claim wherein (l) is Cl AlCH AlCl and (2) molybdenumacetylacetonate.

31. A catalyst of claim 1 wherein (1) is CI AICH AICI and (2) titanylacetylacetonate.

32. A catalyst of claim 1 wherein l) is Cl A1CH AlCl and (2) zirconiumacetylacetonate.

33. A catalyst of claim 1 wherein (1) is Cl AlcH AlCl and (2) nickelacetylacetonate.

34. A process for preparing a catalyst useful for polymerizationconsisting essentially of admixing in a. solvent (1) a compound of theformula wherein 'M is boron, a Group II or III-A metal of the PeriodicTable, X is a halogen atom and n is one less than the valence of M and(2) a compound of transition metal of Groups III-B, IV-B, V-B, VI-B,VII-B, VIII or I-B of the Periodic Table in proportions such that themolar ratio of compound (1) to compound (2) lies in the range from about0.3:1 to about 200:1.

References Cited UNITED STATES PATENTS 4/1966 Shearer et al. 252429 A XOTHER REFERENCES PATRICK P. GARVIN, Primary Examiner US. Cl. X.R.

252429 B, 429 C, 430, 431 R; 260--88.2 R 94.9 B, 94.9 CA, 94.9 CB

